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The Colombian was involved in all three goals after winning the penalty which Robert Lewandowski converted for the opening goal before his deft chip saw Arturo Vidal fire home.
After five games, the victory in Gelsenkirchen put defending champions Bayern top for the first time, but Borussia Dortmund can regain the lead if they win at Hamburg on Wednesday.
The away win was a boost for Bayern who confirmed Tuesday that goalkeeper and captain Manuel Neuer had undergone another operation on his left foot and is out until January.
“That wasn’t so easy, but at the end we managed to dominate,” said Neuer’s replacement Sven Ulreich, who now finds himself as Bayern’s first-choice goalkeeper after wanting to quit in the summer.
“Of course it’s a tough situation for the team and Manuel, but we hope he’ll be back soon.”
Bayern coach Carlo Ancelotti rotated the squad with James on the right wing as one of six changes from the side which beat Mainz 4-0 on Saturday.
James won a penalty on 23 minutes when the video assistant referee confirmed his cross had been knocked away by the hand of Schalke defender Naldo.
Lewandowski dispatched the penalty for his sixth goal in five games.
James, who signed a two-year loan deal from Real Madrid in July, then fired home on 29 minutes when Corentin Tolisso’s pass found him with acres of space in the area.
It was a sublime chip over the Schalke defence from James which was then drilled home by Vidal on 75 minutes.
Leipzig stumble
The win left Bayern two points clear at the summit while Augsburg are up to third, with 10 points, after their shock 1-0 home win against RB Leipzig.
Austria midfielder Michael Gregoritsch scored Augsburg’s winner after only four minutes in Bavaria, but Leipzig coach Ralph Hasenhuettl paid the price for making nine changes as his team played poorly.
Belgium striker Divock Origi, on loan from Liverpool, scored his first goal for Wolfsburg in their 1-1 draw at home to Werder Bremen before Fin Bartels equalised.
Origi showed his pace to win a foot race for the ball and stabbed home on 28 minutes as Wolfsburg’s new coach Martin Schmidt, who replaced the fired Andries Jonker on Monday, picked up a point.
Earlier, Brazil striker Raffael scored two second-half goals as Borussia Moechengladbach climbed to seventh after their 2-0 home win at home to Stuttgart.
It was Stuttgart’s first game since captain Christian Gentner suffered multiple facial fractures and concussion in a collision during Saturday’s win over Wolfsburg.
Gladbach’s Raffael opened the scoring by finishing the move he started with a superb 57th-minute goal after releasing Nico Elvedi on the wing and firing home the Swiss right-back’s cross.
Stuttgart defender Dennis Aogo gave away a penalty when he held Belgian forward Thorgan Hazard back in the area and Raffael slotted away the spot-kick on 74 minutes.
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