Chasing 158, the hosts held their nerve to reach the target in the final over, finishing on 158/4. Chloe Tryon applied the finishing touch in emphatic fashion, launching a six off the opening delivery of the 20th over to seal the result, ending unbeaten on 18.
Captain Laura Wolvaardt led from the front at the top of the order, striking a composed 51 from 39 balls after returning to her preferred opening role. She found strong support in Annerie Dercksen, who produced an assured unbeaten 44 off 34 deliveries to guide the chase home.
Earlier, South Africa's bowlers and fielders combined effectively to limit India to 157/7, despite the visitors racing to 46 without loss inside the opening five overs. Disciplined bowling and sharp work in the field helped rein things in after the early momentum.
For India, Shafali Verma made a brisk 34 off 20, while Jemimah Rodrigues contributed 36 from 29. Captain Harmanpreet Kaur anchored the innings with an unbeaten 47 off 33 balls.
With the ball, Ayabonga Khaka was outstanding, claiming 3/16 from her four overs, while Tumi Sekhukhune chipped in with 2/27.
The second match of the five-game series will take place at the same venue on Sunday.