In this study, biochar R550, obtained from rice husk charred at 550 °C, was used to detoxify Cr(VI) and organic pollutant p-nitrophenol (PNP) with the cooperation of sulfite, simultaneously. Cr(VI) was mainly reduced by sulfite, and the reduction was accelerated by biochar. Also, the reactive oxygen species formed in-situ as a result of enhanced oxidation of sulfite with Cr(VI)/R550 system and the activation of O2 by R550, led to the degradation of PNP. Production of the radicals viz., SO3[rad]−, SO4[rad]− and [rad]OH was followed by Electron Paramagnetic Resonance (EPR) study, and the predominant role of SO4[rad]− towards PNP degradation was confirmed by radical quenching tests. The reaction completed biochar sample was undergone the X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) spectral analysis, which suggested that the carboxyl group of the biochar triggered and enhanced the reactivity of Cr(VI) via coordination linkage, which in turn activated the sulfite and converted the SO32− into SO4[rad]− to a higher extent by overcoming the undesirable transformation of SO32− to SO42−. Such results could also be verified by the other three biochar (Oxi-R550, H-R550, and R800). The results of the present study shed light on the mechanism of biochar mediated sulfite activation process by Cr(VI) and also assured the viability and green approach of the technique in detoxifying the industrial effluents containing Cr(VI) and organic pollutants.