Abstract Two‐dimensional (2D) lateral heterostructures have emerged as a hot topic in the fast evolving field of advanced functional materials , but their fabrication is challenging. The layer‐structured WS 2 was theoretically demonstrated to be inert to oxidation except for the monolayer, which can be selectively oxidized owing to the simultaneous interaction of oxygen with both sides. Combined with the theoretical calculations, a new method was developed for the successful construction of 2D lateral heterostructures of WS 2 /WO 3 ⋅H 2 O in an ambient environment, based on a simple liquid‐phase solution exfoliation. These lateral heterostructures of WS 2 /WO 3 ⋅H 2 O have interesting properties, as indicated by enhanced photocatalytic activity toward the degradation of methyl orange (MO).