Earlier, star world No.6 Tsitsipas defeated de Minaur 6-3, 7-5 in a brilliant contest to bring the tie to 1-1.
De Minaur was outclassed from the start of the match as Tsitsipas broke him in the second game, and then again in the sixth game after the Australian had broken back.
The 22-year-old Greek star – despite that one loss of serve – dominated with his supreme ground strokes, the highlight a sweet backhand down the line to take the score to 5-2 in the first set.
Tsitsipas’ prediction that de Minaur would struggle on his serve and with his volleying proved true in the first set, with the 21-year-old proving too weak on the former and sloppy on the latter. There were also too many unforced errors.
However, as always, he did show spirit, and a lot of it helped him not get blown out of the water, getting shots back when Tsitsipas was well on top in rallies in the second set.
He also excelled when aggressive later in the second set, thankfully cleaning up errors off his forehand.
But Tsitsipas saved a set point at 5-4, and then de Minaur missed an easy volley to lose that game, which was followed by a break for the Greek off the back of two unforced errors from the Australian. Tsitsipas then served out the match.
In the first match, Millman bounced back from a trouncing at the hands of Spain’s Pablo Carreno Busta to defeat Pervolarakis 6-2, 6-3 and get Australia off to the perfect start.
Millman looked rusty against the world No.16 Spaniard on Tuesday night but on Wednesday night – facing a milder test against the world No.462 Pervolarakis – found matters much easier.
The world No.38 took more risks and looked to hit down the line more regularly and it paid off, pushing his opponent into uncomfortable areas early.
Millman could not afford to sleep on the 24-year-old though, the pair played in the ATP Cup last year and it took three sets and a tie-break to hand the Australian the win on that occasion.
However, this time Pervolarakis had lost eight matches in a row before coming to Rod Laver Arena and he looked suitably out of sorts at times.
Millman broke in the fourth game of the first set, after the initial exchanges were a bit like a war of attrition, and never looked back, the break secured with a nice cross-court forehand from deep behind the baseline.
He held a double deuce game to make it 5-2 and then broke again to win the set 6-2.
The Queenslander then broke his rival in the fourth game of the second set to open up a 3-1 lead, which was never overcome, Millman’s confidence growing as the match wore on with his winner tally and second serve efficiency increasing too.
In the night’s other tie between Russia and Japan, Andrey Rublev made light work of his opponent Yoshihito Nishioka, 6-1, 6-3 to give Russia an early lead. Kei Nishikori then lost to Daniil Medvedev 6-2, 6-4.
Anthony is a sports reporter at The Age.