Zverev knew a victory over Hurkacz would see him through to the semi-finals from the Red Group along with Daniil Medvedev and the third seed duly prevailed 6-2 6-4.
The 2018 champion did not face a break point as Hurkacz bowed out after losing all three matches on his debut at the season-ending tournament in Turin.
Zverev's commanding win also ended alternate Jannik Sinner's hopes of qualifying on home soil at the Pala Alpitour.
The German will do battle with world number one Djokovic for a place in the final after losing only 11 points behind his serve in his final round-robin match.
Zverev got off to a storming start and never looked back, surging into a 4-0 lead in the opening set and breaking once in the second to put himself two wins away from claiming the title for a second time.