Wormlike GdFeO3 (GPO) nanoparticles were synthesized by a glycol-assisted sol-gel rapid calcination process. The as-synthesized GdFeO3 was characterized by X-ray diffraction, transmission electron microscopy, differential scanning calorimeter and thermogravimetric analysis, Fourier transformed infrared spectroscopy, and UV-vis absorption spectroscopy. The visible-light-responsive photocatalytic activity of GdFeO3 nanoparticles was evaluated by the photodegradation of Rhodamine B under visible light. The synergism of semiconductor-photocatalyzed oxidation and heterogeneous photo-Fenton-like reaction can markedly promote the photodegradation with a booming catalytic activity (k = 1.2814 h(-1)). Compared with the bulk, the catalytic activity of the GFO-H2O2 system was improved about 80 times. Meanwhile, the glass carbon electrode decorated with the resulting nanoparticles was used to examine the electrocatalytic behavior for p-nitrophenol reduction in a basic solution. The results show the obtained GdFeO3 nanoparticles with excellent photocatalytic and electrocatalytic activities.