Coming off a resurgent 2006 in which won five tournaments on the LPGA Tour, including her second Kraft Nabisco Championship, Webb eagled the par-5 16th -- her second eagle of the day -- to pull within a stroke of Kemp.
But Webb missed an 11-foot birdie putt on 18 that would have put her into a tie for the lead. She is attempting to win her third Australian Open title.
Making her first start of the year, Webb said she was nervous.
'I just all of a sudden realized that it was the first tournament round of the year,' she said, 'and I was thinking, 'I don't know if I'm ready for this.''
But she curled in an improbable 70-foot eagle putt at the second.
Before the putt, Webb said she turned to her caddie Mike Paterson and said, 'You have to give me 50 bucks if I get this within 5 feet.'
The ball climbed the second of two mounds and almost came to a stop before it went down the slope toward the hole. It kept going, and when it fell into the cup Webb looked more embarrassed than happy.
'If you don't play a tournament for a couple of months you wonder if you've still got it,' Webb said. 'Obviously the bomb that I made on the second settled me down.'
Kemp is a regular on the Ladies European Tour, which is co-sanctioning the event at Royal Sydney. Playing the back nine first where she finished 2-under 34, the 21-year-old birdied the first, second, fourth and fifth holes to start her final nine.
Kemp is often compared with Webb as the next star Australian golfer.
'It's a compliment,' Kemp said. 'That's flattering that people could think that. But there's no pressure. What happens, happens. I'll just go out there and play my game.'
Campbell, who earned more than $400,000 on the Japanese tour last year, had a 7-under 29 on her first nine holes. But bogeys on the third and ninth holes gave her a 2-over 38 on her final nine for a 67.
'It was a dream nine holes,' Campbell said. 'Putts went in, I hit it straight, it all seemed to fall into place and before I knew it I was 7 under.
'I was a bit nervous (on the last nine) because obviously you don't do that every day.'
Wei Yun-jye of Taiwan shot a 68 and is alone in fourth. Amy Yang, an Australian-based South Korean who won last year's ANZ Australian Ladies Masters, is tied with two others at 69, three shots back.
World Match Play Championship winner Brittany Lincicome of the United States had a 70 and is tied for ninth. Laura Davies of Britain, who won the Australian Open when it was last played in 2004, shot a 73.
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