Poly (3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) stands out as a renowned commercial conducting polymer composite, boasting extensive and promising applications in the realm of film electronics. In this study, we have made a concerted effort to overcome the inherent drawbacks of PEDOT:PSS films (especially, high moisture absorption, mechanical damage vulnerability, insufficient substrate adhesion ability, etc.) by uniformly blending them with polydimethylsiloxane polyurea (PDMS-PUa) and silica (SiO₂) nanoparticles through a feasible mechanical stirring process, which effectively harnesses the intermolecular interactions, as well as the morphological and structural characteristics, among the various components. The Si−O bonds within PDMS-PUa and the −CH₃ groups attached to Si atoms significantly enhance the hydrophobicity of the composite film (as evidenced by a water contact angle of 132.89° under optimized component ratios). Meanwhile, SiO₂ microscopically modifies the surface morphology, resulting in increased surface roughness. This composite film not only maintains high conductivity (1.21 S/cm, in contrast to 0.83 S/cm for the PEDOT:PSS film) but also preserves its hydrophobicity and electrical properties under rigorous conditions, including high-temperature exposure (60–200 °C), ultraviolet (UV) aging (365.0 nm, 1.32 mW/cm²), and abradability testing (2000 CW abrasive paper, drag force of approximately 0.98 N, 40 cycles). Furthermore, the film demonstrates enhanced resistance to both acidic (1 mol/L, 24 h) and alkaline (1 mol/L, 24 h) environments, along with excellent self-cleaning and de-icing capabilities (−6 °C), and satisfactory adhesion (Level 2). Notably, the dried composite film can be re-dispersed into a solution with the aid of isopropanol through simple magnetic stirring, and the sequentially coated films also exhibit good surface hydrophobicity (136.49°), equivalent to that of the pristine film. This research aims to overcome the intrinsic performance drawbacks of PEDOT:PSS-based materials, enabling them to meet the demands of complex application scenarios in the field of organic electronics while endowing them with multifunctionality.