The US pair took a silver medal in Vancouver, as Canadian couple Tessa Virtue and Scott Moir clinched gold, but Davis and White are the form duo coming into the Games.
And, last to take to the ice in Sunday's short dance section of the competition, the duo posted a total segment score of 78.89 to lead overnight.
Virtue and Moir had sat on top of the leaderboard until the American routine and they are 2.56 points behind their rivals heading into Monday's free dance.
Next are Elena Ilinykh and Nikita Katsalapov, who will be looking to please the home crowd on Monday by adding to Russia's three figure skating medals in Sochi.
The French pair of Nathalie Pechalat and Fabian Bourzat lie in fourth at this stage, 6.11 points off the leaders.
And British duo Penny Coomes and Nicholas Buckland missed out on a top-ten qualification, heading into Monday's free dance in 11th after the judges penalised them for an extended lift, leaving a score of 59.33.