again in set two to lead 2-0 before Thiem held on to pull to with in 3-2.
With Zverev serving at deuce, Thiem netted a forehand before the German struck an overhead winner to hold serve and take a 4-2 set two lead.
Both players then held their serves with Zverev maintaining the lead at 5-3.
An aggressive game from Thiem saw him pull to within 5-4 after he struck two aces and two groundstroke winners.
Serving for the match, Zverev went ahead 15-0 before Thiem struck an inside out down the line forehand wide to trail 30-0.
The German committed a forehand error to reach 30-15 before striking a crosscourt forehand winner to set up double match point at 40-15.
Thiem sent a backhand return long to end the match after one hour and 18 minutes of play.
The 21 year old Zverev, who dominated the Madrid tournament, did not drop a set or face a breakpoint all week.
The German will defend his 2017 Rome championship tournament victory this week as the defending champion.
"Hopefully I can continue this kind of streak in Rome," he said.
"Winning two titles in two weeks is great. Winning a Masters, another Masters, is unbelievable. But before the French Open, there's still Rome where I'm the defending champion.
"Obviously, I didn't get broken one time [in Madrid]. But I don't think I faced break points in the whole tournament. For me,
this is an amazing stat to know in the back of my mind."
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