TiO2 nanotube arrays (TNA) have been modified by cobalt phosphate (CoPi) through potentiostatic electrodeposition method. Different samples have been prepared by changing the loaded CoPi through the deposition time from 10 to 960 min. Formed catalytic materials have been characterized by different methods. Although charge transfer resistance of the CoPi/TNA photoanodes have been decreased from 5.5 to 4.0 k Omega by increasing the deposition time from 5 to 60 min, the maximum photoresponse was obtained for 10 min CoPi deposition leading to 24% more photocurrent compare to bare TNA which proposed optimum value for cobalt phosphate decoration. Based on field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) results, by depositing the electrocatalyst, nanotube walls have been spread and holes have been covered by CoPi. Correlation between observed change in surface morphology and Raman spectra of the samples along with electrocatalytic tests revealed how decoration time can influence structural properties and photoelectrochemical performance of the final CoPi/TNA photoanodes in solar water splitting system.