An ominous start for Nadal saw Zverev break in the first game of the match, with a poor drop shot into the net and a double fault from the Spaniard heavily contributing.
Each mistake by Zverev early on was cheered by the pro-Nadal crowd and, after saving two break points for a 3-1 lead, the German exerted his control before breaking again for the set.
Nadal, playing with more aggression and intensity, raised hopes again by moving into a 4-2 second-set lead.
But as quickly as belief increased, Zverev took it away.
The Olympic champion remained composed, upping his level in the 10th game to break back with some precise ball-striking.
The gravitas of the occasion was illustrated by Nadal’s great rival Djokovic, along with defending women’s champion Iga Swiatek and Wimbledon men’s champion Carlos Alcaraz, sitting in the stands to watch.
Like the second set, they watched Nadal move a break up in the third before buckling again under more pressure as Zverev stormed back from 2-1 down to 4-3 in front.
Nadal, as he has always done in his illustrious career, refused to give up and created two break points in the eighth game, but Zverev came through in a strong finish.
“The first round wasn’t the ideal one, but I was competitive, I had my chances,” said Nadal.
“But it was not enough against a great player.”