The $1.6 million LPGA match-play event starting Thursday pits eight four-woman national teams in quest of global bragging rights, with a trophy and crowns of supremecy for the winners.
Seventh-ranked Webb has a chance to play for her nation after years of looking longingly at US-Europe duels in the Solheim Cup, settling for a role as US team cart driver and snack fetcher.
"It probably made me want to play more than be a cart driver and look after the Americans and drive and get Dairy Queen smoothies," Webb said.
"For me to be able to wear our Australian colors and play under the Australian flag is something that's very special."
Australia will face South Korea in Thursday's opening best-ball matches with Aussies Katherine Kirk and Lindsey Wright facing Park In-Bee and Ryu So-Yeon while Webb, 39, and Lee, 18, play Choi Na-Yeon and I.K. Kim.
Two-time Australian Women's Amateur champion Lee plans to turn professional late this year. Webb says the Perth prodigy can handle the challenge now.
"Minjee, she's ready to play out here full time," Webb said. "Of the four of us, Minjee knows me the best, so I felt that to ease her into the competition, it was probably best she play with me.
"For me, it's a pretty cool experience, too, that a couple of years ago she was coming over to stay with me at the US Open and now she's ready for the world stage. So it will be a fun day."
Lee is happy to be able to learn from a legend such as Webb, whose major debut in 1996 came two months before Lee was born.
"She's kind of like mom on tour, well not mom but auntie I guess -- she's not that old," Lee said.
"She just kind of helps me out whenever I kind of get stuck or whenever I have a question, I ask her and she's pretty good about it. She just kind of answers whatever she can."
- Aussies indecisive -
Lee said she felt comfortable in the world-class company and Kirk, ranked 35 spots below her at 108th, agreed.
"She should be comfortable. She has a world ranking better than two on our team," Kirk said. "Minjee has probably played more match play than Karrie, Lindsey and I recently so we jokingly designated her as the captain."
With no actual captain, Webb tries to play down the leader role that would flow naturally from her seven major titles and 57 career crowns, two of them this yeat.
"We're all very indecisive," Webb said. "I mean it took us about 20 minutes to decide where we were going to dinner the other night, so no one's really making any assertive calls out there."
Future pairings likely won't get easier.
"I would really like to play with everybody this week. I think that would be really fun," Webb said.
"But in saying that, if we play really well tomorrow, it would be hard to change the pairings up. So we have left that option open."