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The vice presidential debate is set to take place at Longwood University in Virginia.
Observers expect Kaine to hammer Pence over running mate Donald Trump's various controversial statements and policy positions, while Pence is expected to deflect criticism and focus on Hillary Clinton's shortcomings.
With no specific policy topics outlined, the debate will be divided up into nine, 10-minute segments about a range of topics.
Both candidates have been prepping for the debate for weeks.
Pence enlisted Wisconsin Gov. Scott Walker to play Kaine in debate prep, while Kaine faced off against experienced debate stand-in Robert Barnett, a high-powered lawyer from Washington, DC.
The debate begins at 9 p.m. ET.