A nail-biting finish saw Belgian team Omega Pharma-Quick Step overturn provisional leaders Liquigas at the top of the standings with a time of one hour, three minutes and 17.17 seconds before waiting for the Swiss-based team BMC to complete the demanding 53.2km course to the Dutch town of Valkenburg.
But where Omega Pharma-Quick Step mastered the final ascent of the Cauberg with aplomb to cross the line with a full quota of six riders, BMC fragmented and had to regroup with the four requisite riders ahead of the final flat run into the finish.
Despite a brave effort, BMC were 3.23 seconds off the blistering pace set by gold medallists Omega Pharma-Quick Step.
Australian team Orica-GreenEdge completed the podium with a solid ride for third place - but it was a day to forget for the British team Sky Procycling, who could only manage the ninth best time in the absence of its main stars, including Tour de France winner Bradley Wiggins and runner-up Chris Froome.
Sunday's TTT was the first time the World Championships had run a team time trial in such a format. The last time the Worlds included a TTT as part of its programme was back in 1994, where teams of four riders represented their country over a long 100km course.
The revamped Worlds TTT saw squads of six riders compete not for their home country but for their commercial teams.
Although held in the Netherlands, renowned for its flat countryside, the TTT course rolled through the hilly Limburg region and featured three climbs including the legendary Cauberg - best known for its annual appearance at the conclusion of the Amstel Gold spring classic.
Forty teams - including a number of Pro Continental and Continental outfits - took part in the 53.2km race-against-the-clock, starting with MTN Qhubeka, South Africa's first ever Pro Continental team and one that hit the headlines this week with the signing of German sprinter Gerald Ciolek from - incidentally - Omega Pharma-Quick Step.
Italian team Liquigas-Cannondale - featuring Italy's Vincenzo Nibali and Slovakian Peter Sagan - held the lead for a large part of the afternoon after a tight ride ahead of most of their World Tour rivals.
Cheered on by swathes of Dutch fans, home favourites Rabobank set off to a pulsating start - posting a landmark time at the first check that would not be beaten throughout the afternoon.
But a spectacular implosion riddled the Dutch team on the final climb of the Cauberg, with Stef Clement and Lars Boom riding so hard that the two remaining Rabobank riders - Luis Leon Sanchez and Robert Gesink - could not keep up.
The team regrouped but could only take provisional second place, three seconds off the pace set by Liquigas. With the favoured teams still yet to arrive, the chance of a Dutch team securing a podium place looked small - especially with Vacansoleil-DCM also struggling.
Liquigas's long tenure in the winning enclosure was brought to an end by Omega Pharma-Quick Step who shaved more than a minute off the Italian team's time after arriving with all six riders as one - Belgians Tom Boonen and Kristoff Vandewalle, Frenchman Sylvain Chavanel, Germany's reigning world time trial champion Tony Martin, Dutchman Niki Terpstra and Peter Velits of Slovakia.
As Omega Pharma-Quick Step moved into the leaders' enclosure there were just three more teams left on the road: BMC, GreenEdge and a faltering Team Sky, who had been well off the pace at every check point.
BMC started the Cauberg with six riders but quickly lost two on the early slopes of the punchy 5.8 percent climb. As American youngster Tejay van Garderen rode off the front, his countryman Taylor Phinney struggled to maintain his rhythm and needed to be paced back by Belgian Philippe Gilbert and Italy's Alessandro Ballan.
The four riders eventually came back together ahead of the final dash to the line - but the damage had been done, BMC crossing the line just 3.23 seconds behind winners Omega Pharma-Quick Step to take the silver medal.
Orica-GreenEdge, also reduced to just four riders, kept their composure to secure the bronze medal, the Australian team finishing 47.06 seconds down on the winners to cap off an impressive first season in the World Tour.
RadioShack-Nissan, Team Sky and Garmin-Sharp - usually forces to be reckoned with in TTTs - struggled over the course and finished eighth, ninth and tenth respectively.
Sky's six-man squad did not feature British time trialling heavyweights Wiggins or Froome, nor did it include Australian duo Michael Rogers and Richie Porte. Instead, there were places for British trio Alex Dowsett, Ian Stannard and Geraint Thomas, as well as Colombian Sergio Henao, Spaniard Juan Antonio Flecha and Norway's Edvald Boasson Hagen.
Earlier in the day, favourites Team Specialized - Lululemon won the women's team time trial over a shorter 34.2km course. The German-registered team completed the course in a time of 46 minutes and 31.63 seconds. Australian team Orica took the silver, 24.19 seconds in arrears, while Dutch team AA Drink - Leontien.nl Cycling completed the podium, just under two minutes behind.
The men's 45.7km elite ITT takes place on Wednesday, a day after the women's 24.3km elite time trial.
World championships TTT top ten: 1. Omega Pharma-Quick Step 1:03:17.17, 2. BMC +3.23, 3. Orica-GreenEdge +47.06, 4. Liquigas +1:04.73, 5. Rabobank +1:08.13, 6. Movistar +1:18.13, 7. Katusha +1:18.57, 8. RadioShack-Nissan +1:21.22, 9. Sky Procycling +1:32.33, 10, Garmin-Sharp +1:35.13.