Angus Robson made a fine 75 but Gary Wilson's unbeaten 160 put his Surrey side in a strong position after two days of the LV=CC game at the Kia Oval.
Captain Wilson batted for eight minutes short of six hours to compile his third first-class hundred, his previous highest score of 125 having been compiled against the same opponents in 2010 at Grace Road.
Together with Chris Tremlett, whose 90 was also a career best, he added 192 for Surrey’s eighth wicket, a new county record against Leicestershire beating the 141 complied by Alistair Brown and Alex Tudor at Oakham School 14 years ago.
Irishman Wilson then inflicted further punishment on a tiring attack by putting on an unbroken 82 in 15.5 overs with last man Jade Dernbach before Surrey declared 30 minutes before tea on 522 for nine, the second time this season they have scored more than 500.
That left Leicestershire needing 373 just to avoid the follow on and a fine innings by in-form opener Robson helped County reach 125 for three at stumps. The deficit therefore stands at 397 at the halfway stage of the game.
Robson said: "I felt pretty good out there. The plan was to try and bat smart. It was important not to get bogged down against a very good attack.
"It's a shame I got out when I did because it was a good opportunity to get a big score for myself and, more importantly, the team."
A flat pitch meant Wilson and Tremlett batted with few alarms before lunch as they extended their partnership with 91 runs in the session.
Tremlett passed his previous highest score of 64, made for Hampshire in 2005, before Wilson moved into the 90s with successive boundaries off Ben Raine (24-4-87-2).
They had put on 192 in 63 overs when Tremlett mistimed a pull off Raine in the 134th over and was caught by Nathan Buck at long leg after facing 183 balls and hitting a six and ten fours.
Wilson reached his hundred in slightly fortuitous fashion when he top-edged a sweep off Dan Redfern and the ball flew over wicketkeeper Niall O’Brien.
He lost Matthew Dunn for a four-ball duck shortly after when Redfern (11-2-36-1) turned one just enough to have Surrey’s No.10 caught off bat and pad by Matthew Boyce at short leg.
But if Leicestershire thought the end was in sight, Wilson and Dernbach had other ideas. The captain moved past his previous highest score with Dernbach offering solid support before Wilson called time to allow his new-ball attack a burst before tea. His own contribution came off 296 balls with 21 fours and a six.
Other bowling figures: Charlie Shreck 32-9-81-1, Nathan Buck 25-5-101-1, Jigar Naik 30-6-106-1, Rob Taylor 27-8-81-3, Robson 3-0-11-0.
County got through to tea but Tremlett and Wilson formed another partnership early in the evening session to inflict more pain on Leicestershire. Tremlett, who was capped at tea alongside Vikram Solanki, celebrated that achievement by having Boyce (2, 20b) pouched by Wilson behind the stumps with the score on 26.
Ned Eckersley (4, 22b) was leg before to Dernbach at 47 for two but the increasingly assured Robson, whose brother Sam posted a maiden Test hundred in just his third innings for England at Headingley on Saturday, added 73 with Redfern (25*, 67b). The opener drove powerfully on both sides of the wicket.
They looked to have seen their side to stumps, but in the penultimate over after a short break while the floodlights were switched on, Robson was lbw to Dunn 25 short of his maiden first-class century, made off 112 balls with 12 fours. It ended a fine stand worth 73 with Redfern.