James grabbed her third goal of the tournament after halftime before Chloe Kelly and Rachel Daly also found the net to give England an emphatic victory as they head off to Brisbane to play Nigeria on Monday for a place in the quarter-finals.
It was a record World Cup defeat for Asian champions and 1995 semi-finalists China, who exit in the group stage for the first time in eight appearances at the global showpiece.
Without the injured Keira Walsh as the holding midfielder, England shifted to a 3-5-2 formation and were soon making good inroads down the flanks.
England opened the scoring with a move that started with a Lauren Hemp cross from the left, James heading the ball to Russo in the box and the forward bringing it down before sliding it inside the post.
James was finding it hard to find space to show her skills on the edge of the box but, fed by Millie Bright storming out of defence, slid a pass from a deeper position through to Hemp in the 26th minute.
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The Manchester City forward took what seemed to be an extravagant first touch but her pace took her clear of the last defender and she finished crisply.
The third goal came in the 41st minute when James was left completely unmarked on the edge of the box at a free kick and clipped the ball first time into the back of the net.
James conjured up an even better finish for what would have been a fourth goal of the tournament in stoppage time at the end of the half but it was ruled out for offside after reference to VAR.
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China had offered little in attack but got a goal back through a Wang Shuang penalty at the start of the second half after VAR adjudged defender Lucy Bronze had handled in a goalmouth scramble.
James, however, grabbed the spotlight again in the 66th minute when Jess Carter’s cross picked her out at the far post and she finished with a beautifully controlled volley.
Substitute Kelly then scored the fifth into an empty net from a James through ball that China goalkeeper Zhu Yu completely misjudged and wingback Daly put a gloss on the scoreline with a fine finish in the 84th minute.
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“Again, another day of what dreams are made of,” said James. “I’m happy for the team and everyone’s buzzing. And yeah, we’re looking forward to going into next round.”