Seventh-seeded North Carolina (29-5) will face fifth-seed UCLA in the national title match on Tuesday at 1 p.m.
A spot in the finals came down to the singles match on court one between the Tar Heels' top ranked Jamie Loeb and Stanford's third-ranked Kristie Ahn.
Ahn outlasted Loeb in the opening set, winning the tiebreaker 7-4 for the 7-6 win.
Loeb picked up a break point to start the second set and was unflappable from that point, winning 6-0 and 6-0 in the final two sets to send the Tar Heels into their first title match in program history.
Carolina made a dramatic comeback on court one to earn the doubles point and a 1-0 advantage over the defending national-champion Cardinal.
UNC raced to an 8-2 victory on court two as the 13th-ranked duo of Whitney Kay and Caroline Price improved to 22-6 on the season, downing Stanford's 50th ranked team of Taylor Davidson and Ellen Tsay.
The Cardinal knotted the doubles portion of the match with an 8-4 win on court three, meaning the deciding point would come down to court one.
Ahn and Carol Zhao of Stanford, ranked 10th in the country, jumped out to a 5-2 lead, but the third-ranked tandem of Hayley Carter and Loeb stormed back with the final six points to earn an 8-5 victory. The dynamic freshmen duo improved to 32-4 on the season.
Carter made it 2-0 in favor of the Tar Heels with a 6-2, 6-1, victory on court two over No. 51 Krista Hardebeck.
Stanford got on the board with a win on court four, but No. 59 Caroline Price swung the momentum back in favor of the Tar Heels with a 6-4, 6-4, victory on court three over No. 21 Carol Zhao.
Within minutes of each other, Stanford picked up wins on courts six and five, respectively, to knot the match at 3-3.
Loeb's win was the 50th on the season for the freshman from Ossening, New York. Fellow rookie Carter is now 46-6.
Women's Semifinal: #7 NORTH CAROLINA (29-5) def. #11 STANFORD (20-3), 4-3 - McWhorter Courts
Doubles (Order of finish: 2,3,1)
1. #3 Jamie Loeb/Hayley Carter (NORTH CAROLINA) def. #10 Kristie Ahn/Carol Zhao (STANFORD), 8-5
2. #13 Whitney Kay/Caroline Price (NORTH CAROLINA) def. #50 Taylor Davidson/Ellen Tsay (STANFORD), 8-2
3. Caroline Doyle/Krista Hardebeck (STANFORD) def. Ashley Dai/Tessa Lyons (NORTH CAROLINA), 8-4
Singles (Order of finish: 2,4,3,6,5,1)
1. #1 Jamie Loeb (NORTH CAROLINA) def. #3 Kristie Ahn (STANFORD), 6-7(4), 6-0, 6-0
2. #5 Hayley Carter (NORTH CAROLINA) def. #51 Krista Hardebeck (STANFORD), 6-2, 6-1
3. #59 Caroline Price (NORTH CAROLINA) def. #21 Carol Zhao (STANFORD), 6-4, 6-4
4. #50 Taylor Davidson (STANFORD) def. Whitney Kay (NORTH CAROLINA), 6-3, 6-2
5. #54 Ellen Tsay (STANFORD) def. Kate Vialle (NORTH CAROLINA), 6-2, 7-6(4)
6. #57 Caroline Doyle (STANFORD) def. Tessa Lyons (NORTH CAROLINA), 6-2, 6-3