Silicotungstic acid (SiW) decorated reduced graphene oxide (rGO) nanocomposite (rGO-SiW) has been prepared and evaluated as a heterogeneous nanocatalyst for the degradation reactions of methylene blue (MB) and rhodamine B (RhB). The structural and morphological properties of rGO-SiW nanocomposite were investigated by various techniques such as Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), Atomic force microscopy (AFM) and Scanning electron microscope (SEM), which revealed the homogeneous and noncovalent anchoring of SiW nanoparticles on rGO sheets. The catalytic activity of rGO-SiW nanocomposite on the degradations of MB and RhB has been monitored using UV–visible absorption spectrometry in the presence of NaBH4 as the reducing agent at room temperature in water. The reduction reactions followed pseudo-first order kinetics and degradation were achieved in 34 min for MB and 81 min for RhB using rGO-SiW as catalysts.