Schofield is the first name on this season's maiden team sheet, and the 30-year-old is joined by Lions captain Paul Robinson, whose fierce effort to make it 3-0 completed a torrid afternoon for James.
Robinson is joined in defence by New Zealand's World Cup star Tommy Smith and James O'Connor, who both also scored to help Ipswich and Doncaster to away victories over Middlesbrough and Preston respectively.
And Coventry's Richard Keogh, a rock in defence against Portsmouth, completes the back four.
The Spurs loanee takes his place in midfielde alongside QPR's 21-year-old midfielder maestro Adel Taarabt, instrumental in the 4-0 demolition of Barnsley, and Crystal Palace's Darren Ambrose who, after signing a new contract, helped the cash-strapped south Londoners to opening day victory over Leicester.
But former Ipswich, Newcastle and Charlton man Ambrose's performance was bettered by whiz kid Wilfred Zaha, who got Palace underway in their 3-2 win.
And Zaha leads the line with Fredy Eastwood, who got his campaign off to the perfect start by bagging a deadly double to down Pompey and ensure the stricken Championship new boys have more to worry about than just their off-field woes.
Kasper Schmeichel completes the line-up between the sticks after producing a string of fine saves to ensure it wasn't an embarrassing return to the Championship for Leeds, who lost 2-1 to Derby at Elland Road.
Kasper Schmeichel (Leeds United)
Paul Robinson (Millwall)
Tommy Smith (Ipswich Town)
James O'Connor (Doncaster Rovers)
Richard Keogh (Coventry City)
Danny Schofield (Millwall)
John Bostock (Hull City)
Adel Taarabt (Queens Park Rangers)
Darren Ambrose (Crystal Palace)
Wilfred Zaha (Crystal Palace)
Fredy Eastwood (Coventry City)