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n‐type ZrS3 , a semiconductor with a bandgap of approximately 2.1 eV turned out to be a photoelectrochemical material with large anodic photocurrents and low dark currents. In contrast to ZrS2 , normalCdS , and many other sulfides which derive their valence band mainly from sulfur p‐states, ZrS3 is interestingly not photo‐oxidized to molecular sulfur and metal ions. Instead, there is a photoreaction involving water, and the originally bright red crystal is gradually converted into a white one containing oxygen without losing much of its original shape and consistency. The occurrence of sulfur in the form of S22− in this material, as well as the possibility of intercalating oxidation products of water, is considered the reason for this particular photo‐oxidation mechanism. It might open new ways for the understanding and control of photocorrosion.