The ad features clips of Kaine and President Obama, a close friend who'd picked Kaine to be his Democratic National Committee chairman, talking about climate change legislation and coal.
"Our strategy should be take that pie chart, take the coal portion, make it smaller," Kaine says in one clip.
"I'm doing what the president wants me to do," he says in another.
The two are locked in a tight race, though Kaine has had a small lead in most October polling.
Kaine's campaign fired back.
"Given his close ties to mining companies like Peabody Energy that are seeking to strip miners and their families of hard-earned pension benefits, it's no wonder George Allen is hastily trying to change the subject with a misleading, negative attack designed to blur the facts," said Kaine for Virginia Communications Director Brandi Hoffine.
This post was updated at 11:10 a.m.