A recent surge in the study of a room temperature afterglow nanomaterial has surfaced. Considering its natural coverage of a wide emission spectrum and long afterglow with single light excitation have tinkled many multidisciplinary applications. A synthesis of nanosheets with white light phosphorescence at room temperature is arduous. The manuscript emphasizes on the photoelectrochemical response of room temperature proximate white light phosphorescence in boron carbon nitride nanosheets (BCNs), synthesized at consistent physical operands by varying the overall boron dopant. The study thus envisages the interplay of the participating precursors unfolding the physio-chemical interactions between boron/carbon and nitrogen needed towards the phosphorescence phenomenon. BCNs have provided an immense physio-chemical link between the analyte and photoanode under illuminated conditions, as found vital to achieve the reported sensitivity. Three varying boron conditions are examined, out of which, a 1:4 ratio (BCN-2) is distinguished for remarkable afterglow duration. In addition, the as-synthesized BCN-2 has been used for the photo-electrochemical detection of H2O2 via a differential pulse voltammetry method with a limit of detection of 25 nM. The after-glow property has shown a remarkable response toward H2O2 detection. The easy synthesis and reproducibility of these organic phosphors also prompt its propensity to replace commercially available toxic phosphors.