The three-time Melbourne semifinalist was in command for the entirety of the one-hour, 32-minute matchup with Hijikata. With his aggressive ball-striking, he consistently outmatched the World No. 169, hitting 30 winners on the Rod Laver Arena.
After a day of gruelling competition in which the four singles matches could not determine the winner, the Greek pair's 7-6(6), 6-4 win gave their country a 3-2 victory.
Team Greece's star player Tsitsipas, though, persevered to secure victory at RAC Arena, defeating his opponent 4-6, 6-2, 7-6(4) to give his country a 2-0 lead in the Group A match.
The sixth seed clinched a 3-6, 6-3, 6-2 win over the Greek to set up a clash with Casper Ruud in semifinals. Though Rublev was one set down, his groundstrokes helped him clinch his 51st tour-level win of the season.
The current world number 1 Carlos Alcaraz of Spain will be missing the tournament due to an injury. This will leave Nadal, Djokovic, Stefanos Tsitsipas, Casper Ruud, Daniil Medvedev, Felix Auger-Aliassime, Andrey Rublev and Taylor Fritz fighting for the singles title
The top 16 nations' entries have been revealed, with Team Greece, comprised of world No 3 Stefanos Tsitsipas and world No 6 Maria Sakkari, being seeded first.
The Greek player will make his fourth successive appearance at the season finale, which will be held for the second consecutive year at the Pala Alpitour in Turin from November 13 to 20.