The hydrophilic character of chitosan (CS) limits its use as a gate dielectric material in thin‐film transistors (TFTs) based on aqueous solution‐processable semiconductor materials. In this study, this drawback is overcome through controlled crosslinking of CS and report, for the first time, its application to aqueous solution‐processable TFTs. In comparison to natural CS thin films, crosslinked chitosan (Cr‐CS) thin films are hydrophobic. The dielectric properties of Cr‐CS thin films are explored through fabrication of metal–insulator–metal devices on a flexible substrate. Compared to natural CS, the Cr‐CS dielectric thin films show enhanced environmental and water stabilities, with a high breakdown voltage (10 V) and low leakage current (0.02 nA). The compatibility of Cr‐CS dielectric thin films with aqueous solution‐processable semiconductors is demonstrated by growing ZnO nanorods via a hydrothermal method to fabricate flexible TFT devices. The ZnO nanorod‐based TFTs show a high field‐effect mobility (linear regime) of 10.48 cm2 V−1 s−1. Low temperature processing conditions (below 100 °C) and water as the solvent are utilized to ensure the process is environmental friendly to address the e‐waste problem.