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Abstract Understanding psychology is an important task in modern society which helps predict human behavior and provide feedback accordingly. Monitoring of weak psychological and emotional changes requires bioelectronic devices to be stretchable and compliant for unobtrusive and high‐fidelity signal acquisition. Thin conductive polymer film is regarded as an ideal interface; however, it is very challenging to simultaneously balance mechanical robustness and opto‐electrical property. Here, a 40 nm‐thick film based on photolithographic double‐network conductive polymer mediated by graphene layer is reported, which concurrently enables stretchability, conductivity, and conformability. Photolithographic polymer and graphene endow the film photopatternability, enhance stress dissipation capability, as well as improve opto‐electrical conductivity (4458 S cm⁻¹@>90% transparency) through molecular rearrangement by π–π interaction, electrostatic interaction, and hydrogen bonding. The film is further applied onto corrugated facial skin, the subtle electromyogram is monitored, and machine learning algorithm is performed to understand complex emotions, indicating the outstanding ability for stretchable and compliant bioelectronics.