SINGAPORE, February 27, 2014 (AFP) - Webb, disqualified from this month's Australian Ladies Masters for signing for an incorrect score, emerged from the scorer's tent but then hurried straight back inside, fearing she had forgotten to sign her card.
However, all was well and the 39-year-old had correctly signed for a first round of six birdies and no bogeys, enough for a one-shot lead over Caroline Hedwall and Paula Creamer.
"I just had trouble getting out of the scorer tent since then," admitted Webb, referring to the incident in Australia's Gold Coast when she owned up to signing for a 74 instead of a 75.
"So I walked out and couldn't remember if I signed my card, which would have been too late anyway. But before I did an interview and said how happy I was to shoot 66, I wanted to make sure I had signed my card."
Webb made a flying start of four birdies over the first six holes, extending a rich run of form which includes her last-day charge to victory two weeks ago at the Women's Australian Open.
In hot and windy conditions on the demanding, par-72 Sentosa Golf Club course, the 2011 champion picked up two more shots on 14 and 16 to seize an early advantage over the high-quality field.
"I think it's a tricky golf course. I think getting off to the start I did makes you settle down a bit," said Webb, who went round with fellow former winners Shin Ji-Yai and Stacy Lewis, the defending champion.
"My other playing partners struggled to start with and I think this course is one of those courses where if you get on the wrong side of trusting your numbers and positions off the tee, it's a challenging golf course.
"I feel fortunate to get off to such a good start."
Angela Stanford, the winner in 2012, fired four-under 68 to share fourth with Taiwan's Teresa Lu, with Spain's Azahara Munoz a shot further back in lone sixth.
World number one Park In-Bee shot 70, one better than second-ranked Suzann Pettersen who can potentially overhaul the South Korean at the top of the player ratings this week.
New Zealand sensation Lydia Ko, former world number one Tseng Ya-ni and America's Michelle Wie all started the $1.4 million tournament quietly with one-over-par rounds of 73.
Round one scores from the $1.4 million HSBC Women's Champions in Singapore on Thursday (par 72):
66 - Karrie Webb (AUS)
67 - Paula Creamer (USA), Caroline Hedwall (SWE)
68 - Teresa Lu (TPE), Angela Stanford (USA)
69 - Azahara Munoz (ESP)
70 - Amy Yang (KOR), Danielle Kang (USA), Gerina Piller (USA), Caroline Masson (GER), Park In-Bee (KOR)
71 - Ji Eun-Hee (KOR), Choi Na-Yeon (KOR), Brittany Lincicome (USA), Morgan Pressel (USA), Moriya Jutanugarn (THA), Suzann Pettersen (NOR), Ryu So-Yeon (KOR), Lexi Thompson (USA)
Selected:
73 - Lydia Ko (NZL), Michelle Wie (USA), Tseng Ya-ni (TPE)