In this paper, large-scale, self-standing polypyrrole/graphene oxide (PPy/GO) nanocomposite films were prepared by an environmentally friendly and easy-to-operate confined polymerization method, and were also assembled as electrode materials for symmetric all-solid-state supercapacitors. In this paper, large-scale, self-standing polypyrrole/graphene oxide (PPy/GO) nanocomposite films were prepared by an environmentally friendly and easy-to-operate confined polymerization method, and were also assembled as electrode materials for symmetric all-solid-state supercapacitors. The morphology, chemical structure and electrochemical property were characterized by field emission scanning electron microscope (FESEM), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS), respectively. The lamellar structure of GO and both strong interaction with ice and pyrrole could promote polymerization of pyrrole and improve the compactness of the film. With the aid of GO, the conjugation length of PPy increased, the resistance of the material decreased, and the electrochemical energy storage of the composite film was significantly enhanced. In the case of 2.5 wt% GO, the prepared PPy/GO nanocomposite supercapacitor exhibited a high area specific capacitance of 97.3 mF cm⁻² at 1 mA cm⁻². Furthermore, the PPy/GO film supercapacitor also showed excellent cycling stability and good flexibility.