Degradation and delamination resulting from environmental humidity have been technically challenging for poly (3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) thin-film processing. To overcome this problem, we introduced a one-step photolithographic method to both pattern and link a PEDOT:PSS film onto a poly (ethylene glycol) (PEG) layer as a hybrid thin film structure on a flexible substrate. This film exhibited excellent long-term moisture stability (more than 10 days) and lithographic resolution (as low as 2 μm). Mechanical characterizations were performed, including both stretching and bending tests, which illustrated the strong adhesion present between the PEDOT:PSS and PEG layers as well as between the hybrid thin film and substrate. Moreover, the hybrid moisture-absorbable film showed a quick response of its permittivity to environmental humidity variations, in which the patterned PEDOT:PSS layer served as an electrode and the PEG layer as a moisture-sensing element. Perspiration tracking over various parts of the body surface as well as breath rate measurement under the nose were successfully carried out as demonstrations, which illustrated the potential utility of this stable hybrid thin film for emerging flexible and wearable electronic applications.