The comparative study of Ag and Ce doped WO3 modified with GO ternary composites was conducted. Bi-functional promising catalysts were employed for simultaneous Cr (VI) reduction and phenol oxidation as well as hydrogen evolution reaction (HER) through electro catalysis. Both Ag and Ce indicated their effects on orthorhombic WO3. Morphological studies showed big sheets of WO3 were ruptured by foreign materials. C − Ce − W and C − Ag − W surface linkages were analyzed by FTIR and Raman studies. DRS studies indicated that Ce into WO3 alters electronic configuration of WO3. GO/Ag-WO3 showed long absorption tail in visible region. The remarkable quenching of PL intensities is detected in GO/Ag-WO3. GO/Ag-WO3 comparatively produced small onset potential ∼ −175 mV, high current density of ∼75 mAcm−2, small Tafel slop ∼ 46 mV/dec and low charge-transfer resistance (Rct) ∼ 54 Ω. In HER, electronic interaction is strong driving force between WO3 and Ag while GO controls distribution of Ag on WO3/GO leading to fast conduction of charge transfer to improve HER activity. GO/Ag-WO3 composite exhibited elevated photo reduction of Cr (VI) (∼ 86.0 %) and oxidation of phenol (∼ 80.0 %). Trapping test indicated that O2•― and OH• is significant factor for degradation. It provides opportunities of environmentally friendly materials for multipurpose catalytic applications.