The relationship between crystal quality and the properties of indium phosphide nanowires grown on silicon (111) has been studied by transmission electron microscopy, photoluminescence spectroscopy, and photoelectrochemistry. Wires with no defects and with {111} twin boundaries parallel and perpendicular to the growth direction were obtained by metalorganic vapor-phase epitaxy using liquid indium catalyst. Room temperature photoluminescence from the defect-free nanowires is approximately 7 times more intense than that from the wires with twin boundaries. An open-circuit photovoltage of 100 mV is observed for photoelectrochemical cells made with the defect-free nanowires, whereas no photovoltage is recorded for those with twins.