High‐performance transition metal chalcogenides (TMCs) as electrocatalysts for two‐electron oxygen reduction reaction (2e‐ORR) in alkaline medium are promising for hydrogen peroxide (H
2
O
2
) production, but their synthesis remains challenging. In this work, a titanium‐doped zinc–cobalt sulfide hollow superstructure (Ti–ZnCoS HSS) is rationally designed as an efficient electrocatalyst for H
2
O
2
electrosynthesis. Synthesized by using hybrid metal–organic frameworks (MOFs) as precursors after sulfidation treatment, the resultant Ti–ZnCoS HSS exhibits a hollow‐on‐hollow superstructure with small nanocages assembled around a large cake‐like cavity. Both experimental and simulation results demonstrate that the polymetallic composition tailors the d‐band center and binding energy with oxygen species. Moreover, the hollow superstructure provides abundant active sites and promotes mass and electron transfer. The synergistic d‐band center and superstructure engineering at both atomic and nanoscale levels lead to the remarkable 2e‐ORR performance of Ti–ZnCoS HSS with a high selectivity of 98%, activity (potential at 1 mA cm
−2
of 0.774 V vs reversible hydrogen electrode (RHE)), a H
2
O
2
production rate of 675 mmol h
–1
g
cat
–1
, and long‐term stability in alkaline condition, among the best 2e‐ORR electrocatalysts reported to date. This strategy paves the way toward the rational design of polymetallic TMCs as advanced 2e‐ORR catalysts.