Hunter Haas and Tom Scherrer, who each own two Nationwide Tour titles, are one stroke further back at minus-6. They were joined in second by Mark Walker, Jason Allred, Justin Hicks and Michael Letzig.
Bolli got off to a flying start with an eagle on the par-5 first. He came back with birdies on four and eighth to make the turn in minus-4.
The 31-year-old Bolli birdied the par-5 11th at Highland Springs Country Club, then parred the next five holes.
Bolli moved into a share of the lead at 6-under with a birdie on No. 17. He came right back to birdie the par-5 closing hole for the first-round lead.
Last year, Bolli fired four straight rounds of 6-under 66, but it was not enough as he shared third place.
'I guess 65 will be a better number to be stuck on this year,' joked Bolli, the 2004 Chattanooga Classic winner. 'Everything about this course fits my eye. I have a great idea of where I am going to hit the ball off of every tee.'
For the day, he played the four par-5s at minus-5.
'Most of the par-5s are reachable,' said Bolli. 'You have to get after them if you want to contend on this course.'
Haas carded a bogey-free round with six birdies, three on each nine. His solid round came after a session with his coach earlier this week.
'I've never used anyone else. I should probably see him a lot more,' Haas said. 'After Thursday's round, I should see him more frequently. We just fixed a few little things, but it worked.'
Allred and Hicks also posted bogey-free rounds that included six birdies. Scherrer and Letzig had seven birdies to go along with a bogey, while Walker had eight birdies and two bogeys in his round of 66.
Nick Flanagan, who owns wins at the Henrico County Open and the BMW Charity Pro-Am at the Cliffs this year, posted a 5-under-par 67. He shares eighth place with Jacob's Creek Open champion Scott Sterling, Chad Collins, Vance Veazey, Brad Weesner, Troy Kelly, Andrew Pratt and Sam Randolph.
Eight more players, including Franklin Langham and Spike McRoy, are one shot back at minus-4.