Germany made a remarkable comeback to beat defending champions Belgium 5-4 in the sudden death shoot-out after playing a 3-3 in the regulation time.
Belgium beat the last two editions' runners-up Netherlands in a penalty shootout 3-2.
Abhishek and Harmanpreet Singh scored a brace each at the Birsa Munda Hockey Stadium.
India took a 2-0 lead through goals from Shamsher Singh (21st) and Akashdeep Singh (32nd) before Wales stunned the home team with twin strikes in a span of two minutes.
The hosts had earlier started their campaign with a 2-0 victory over Spain.
Amit Rohidas and Hardik Singh scored as the hosts won 2-0.
The veteran goalkeeper will be playing in his fourth World Cup and third at home.
Defender Amit Rohidas has been named Harmanpreet's deputy.
The win sealed India's berth in the 2023-24 Pro League. Gurjit Kaur scored the all-important goal in the sixth minute from a penalty corner.
Harmanpreet now becomes just the fourth player to win the top honour in consecutive years.