In the present study, effect of annealing in Al/nanostructured PS-ML: p+-Si Schottky photovoltaic device is observed for the behavioural change in its pyro-phototronic and corresponding photovoltaic effect. Under UV (365nm) illumination condition, as prepared device shows maximum enhancement and increment factor of 31.16% and 186% at \(0.5V\) compared to the devices annealed at temperature \(\ge 50^\circ C\). However, the coupling between pyro-phototronic and photovoltaic effect remains effective only for the device annealed up to \(100^\circ C\). On further elevating the annealing temperature, the pyro-phototronic effect diminishes while photovoltaic effect remains. The device treated at \(150^\circ C\) shows enhancement in open circuit voltage (\({V}_{oc}\)) value of \(\pm 841 mV\) with large value of fill factor (FF) of \(27\%\) and power conversion efficiency (PCE) of \(9.63\%\) and \(6.36\%\) for upward and downward poling respectively.