We report the structural evolution of BiPO 4 prepared in aqueous under different synthesis conditions viz., templates and temperatures to explore their electrochemical performance for supercapacitor applications. The templates (hexadecyltrimethylammonium bromide (CTAB)), sodium dodecyl sulfate (SDS) were added in bismuth precursor solution at 60 °C, alternatively ethylene glycol (EG), a less toxic additive was incorporated at 90 °C. BiPO 4 exhibits a monoclinic phase, whereas a hexagonal structure was observed with the addition of the templates SDS and CTAB. Interestingly, both monoclinic and hexagonal phases were obtained by the addition of EG. The presence of mixed phase was thoroughly validated through Raman spectra, where vibrational modes for both monoclinic and hexagonal phases of BiPO 4 -EG were witnessed. The effect of template was clearly seen through electron microscopy with a rod-like morphology with (no template) and unfaceted (template). The electrochemical behavior of the synthesized materials was investigated, and it was found that the mixed structure of BiPO 4 -EG exhibited the highest specific capacity (167.15 C g −1 ) at a scan rate of 5 mV s −1 , good capacitance retention at high current densities of up to 10 A g −1 and the lowest electrochemical series resistance (ESR) of 57 Ω. Graphical abstract