Polarization‐sensitive and self‐driven pyroelectric‐based photodetectors have recently gained interest due to their potential application in artificial electronic eyes, biomedical imaging, and optical switches. Here, a photodetector based on light modulation‐induced polarization and depolarization of water molecules on the surface of a 2D MoS2 crystal is reported. The MoS2‐water heterostructure photodetector serves as a self‐driven pyro‐phototronic device that converts light‐induced thermal energy to electrical signals, leading to a transient photoresponsivity as high as 24.6 mA W−1 and a specific detectivity of 2.85 × 108 Jones under 470 nm wavelength at zero bias. Due to the formation of a built‐in electric field at the MoS2‐water interface, this structure also has a high steady–state responsivity of 3.62 A W−1 and detectivity of 9.18 × 108 Jones at 3 V bias, along with a fast response time of ≈0.74 ms. Moreover, due to the rearrangement of the hydrogen bond network in the liquid water upon visible light illumination, the MoS2‐water photodetector is light polarization‐sensitive. The simple fabrication process, low cost, polarization sensitivity, and high performance of the MoS2‐water structure make it an excellent candidate for liquid‐compatible photodetectors.