The performance of photoelectrochemical cell (PEC) strongly depends on the physical properties of photovoltaic material. Polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB) and hexamethylenetetramine (HMT) surfactants were used to modify the morphology nanostructure of ZnO films by a simple technique, namely, ammonia-assisted controlled hydrolysis technique during their growth process. The film treated with PVP, CTAB and HMT produce the nanostructure shape of nanoflower, nanowire and nanorod (NR), respectively. These ZnO samples were utilised as photovoltaic materials in a PEC of FTO (fluorine tin oxide)/ZnO/electrolyte/platinum. It was found that the photovoltaic parameters such as short-circuit current density (J sc ), open-circuit voltage (V oc ) and fill factor (FF) are influenced by the morphology in term of shape and particle size and optical property of the ZnO NR. The PEC utilising the ZnO sample treated with HMT surfactant demonstrated the highest J sc of 0.47 mAcm
À2, V oc of 0.46 V, FF of 29.2% and h of 0.06%, respectively, since it possesses the lowest energy gap.