But when Nadal converted his first break point opportunity and took the second set, the tide officially turned in Spain's favour, with the world number one eventually taking an entertaining 4-6 7-5 6-1 victory to advance to Sunday night's final against Serbia.
And with De Minaur serving at 5-6 for a place in the tiebreak, the unforced errors crept into the Australian's game and Nadal took full advantage to break him on his first break point of the night.
But Djokovic prevailed in the tie-break to give Serbia an unassailable 2-0 lead after Dusan Lajovic had beaten Felix Auger-Aliassime 6-4 6-2.
"Exciting, exhausting, joyful, terrible all at once", was Djokovic's summation. For a moment we both refused to miss the starting point, so it was very rallying and very exhausting. Very physical battle, but also mental battle ... some fantastic points.
The two best players in the world have not met in this new tournament, which began 10 days ago and has gathered momentum from a low base of public recognition. De Minaur took the challenge to him, getting a service break to open and, after missing set points on Nadal's serve in the ninth game, closing out the first set relatively quickly. He deserves to be there.
"Definitely one of the most exciting matches I've played against him or any of the top players in the last few years".
"I feel like the mindset and the intensity I brought out - especially my last two matches, which was the doubles and now this match against Rafa - I felt like I was on another level of intensity and how fired up I got", he said.
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"He changed his game plan a bit more", De Minaur said.
Wary of the obvious threat posed by Djokovic and Serbia in the final, Nadal said on court: "It's going to be a super tough final against Serbia".
"It's never easy to go on court and play good tennis, said Bautista Agut, whose win gave Spain an early 1-0 lead against Spain Saturday night. "... It is possible, however, that he wants to focus on preparing for the Australian Open instead.
"In that match, that's how I felt".
"It's the beginning of the season, and I'm not the only player that feels and talks this way, but I'm very motivated".
Doubles selection will likely come down to how the tie plays out, perhaps the ultimate result seeing the singles split so Nadal and Djokovic face off one more time for the road in Sydney.
Djokovic destroyed a racquet as his form drifted off and his energy stores appeared depleted even though the players were enjoying a respite from the intense heat that has been fuelling bushfires across Australia. "I know I have a complicated game, but if I play at my best level I hope to have my chances".
Djokovic leads Nadal 28-26 in their head-to-head which dates back to 2006.