"I'm excited. It's good to be back on the court, this is such a good time for me", Williams, 36, told Eurosport.
The Florida resident struggled with her movement early on but eventually got into her stride before going down 6-2 3-6 (10-5) to the French Open champion. "It was really nice to be back", said Williams after the match. "But as the match moved on, I was less afraid", explained Williams.
"Knowing that I have won 23 Grand Slam titles and several other titles, I don't think I have anything more left to prove", she said.
Ostapenko is now entered at the 2018 Shenzhen Open, and their exhibition match will be held on 30 December, 5 pm local time.
Williams has registered for the Australian Open, which begins on January 15 at Melbourne Park.
Williams said after the match: "Motherhood is phenomenal. I am definitely looking forward to getting back out there", Williams said.
Having shaken off some cobwebs, Williams then asserted herself, breaking four times to take the second set, with the highlight a crunching forehand return victor off Ostapenko's first serve that kissed the line and left her opponent helpless.
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She clinched the set when she showed off fine athleticism to reach a drop shot which caught the top of the net, but then fell short in the decisive match tie-break, too many errors allowing Ostapenko to clinch victory.
In the super tiebreaker, Ostapenko raced to an 8-2 lead before halting a brief recovery by Williams.
Williams again struggled with her serve in the second set.
Meanwhile, Ostapenko sounded delighted in her official statement, mentioning, "I am thrilled to be playing in Abu Dhabi at the Mubadala World Tennis Championship".
Bautista Agut made a strong start to the second set by breaking Anderson in the second game, but the South African broke back immediately to restore parity.
U.S. Open runner-up Kevin Anderson defeated Spain's Roberto Bautista Agut 6-4, 7-6 (0) in the men's final.