Juli Inkster, a two-time winner of this event, was tied for second with Lorie Kane at 6-under 65. Tracy Hanson finished alone in fourth place at minus 5.
Annika Sorenstam, a six-time champion on the LPGA Tour in 2002, was part of a group at 3-under 68. Defending champion Betsy King also carded a 68, along with Jean Bartholomew, Nanci Bowen and tour rookie Natalie Gulbis.
Dottie Pepper returned to action after shoulder surgery in March, but it was not the homecoming to competitive golf she was looking for. Pepper shot a 4-over 75 to finish 18 holes tied for 118th.
Golden opened her round on the back nine and collected a pair of birdies at 11 and 12. Sensational wedge play led to three late birdies on the front side as she made the turn at 5-under-par 30.
Her solid work with the wedges continued on her second nine. She knocked a 60-degree wedge to six feet to set up a birdie at the third, then made it two in a row with an eight-footer at No. 4.
Golden's lone miscue of the round came at the fifth when she three-putted from 20 feet. She rebounded with an eight-foot birdie putt at the sixth to grab sole possession of the top spot.
'I feel really good. Actually I haven't been really hitting it that great, but I figured out a couple things Wednesday, and it all came together today,' said Golden, who worked on her alignment during the week. 'I'm quite happy.'
Golden earned her first victory on the LPGA Tour last September at the State Farm Classic, where she fired a final-round 63 to hold off Sorenstam.
This season has been a struggle for Golden, who has missed four cuts and whose best finish was a tie for 24th at the LPGA Championship.
'Every once in while a little bam bam, and you shoot a round like today,' said Golden, who briefly gave up golf in 1995. 'I would like to be a little more consistent, but I also try not to get too uptight.'
Inkster flew out of the gate with six birdies on the front side but parred her remaining nine holes. She needed a four-foot par save at 16 and a 10-footer at the 17th to maintain her second-place position.
'Overall I think I played very well,' said Inkster, who won this year's Chick-fil-A Charity Championship. 'I was even on the back, but I had some good shots and good putts and so I am very pleased with my round.'
Kane was flawless on Friday with six birdies and no bogeys. Her putting made the round, as she holed four birdies from over 10 feet.
'I didn't drive it as well as I would have liked, but I did recover well,' said Kane. 'I hit it close and most of my birdies were within 15 feet.'
Full-field scores from the ShopRite LPGA Classic