There was no chance of a let-up from Zverev though and he remained focussed throughout, winning on his first match point when the fifth-seeded Thiem returned long.
Nadal defeated Stan Wawrinka in straight sets a year ago to win the French Open for a record 10th time.
When Petra Kvitova thought she couldn't go on, the Czech hit the critical shots to finally edge Kiki Bertens and claim a record third Madrid Open title on Saturday.
In their third clay court meeting of 2016, Zverev again tasted defeat at the hands of Thiem as the elder man won in four at the French Open 6-7 6-3 6-3 6-3 in the round of 32.
World No. 8 Anderson battled into his first Masters semi-final with a 7-6 (7/3), 3-6, 6-3 win over Serbian qualifier Dusan Lajovic.
Zverev started strongly when Thiem conceded his first service game with a costly double fault.
But the pattern of the match did not alter and a flawless Zverev coasted through the remaining service games to celebrate a huge win in the build up to Roland Garros.More news: David de Gea makes FA Cup claim before final Premier League game
But the Austrian was outplayed, and over-powered, by Zverev, who collects his third ATP World Tour Masters 1000 title.
"In general, the last 10 days have been pretty good, winning two titles in this time", Zverev said.
"Denis came to play today, so I had to step up my game as well", the victor said on-court.
"Obviously I didn't get broken one time (in Madrid)", Zverev said.
Zverev won his eighth career title and second of the season after also winning the Munich Open last weekend.
Edmund lost his cool towards the end of a tight second set when he stopped after a spectator called out, and Shapovalov proceeded to serve an ace. The Austrian also defeated Nadal in the 2017 Rome quarter-finals. Thiem had never beaten Anderson in their six prior FedEx ATP Head2Head matchups, but they had never played on clay, Thiem's surface of choice.
"I was keeping my level up from yesterday, so that was a great thing". I can not be happy that I lost to Thiem in Madrid. "Almost everything worked out".
"Having said this, I think I placed myself in a good position more or less. Now, I'm in the final again, which is unbelievable to me".