An inverted organic bulk-heterojunction solar cell containing amorphous titanium oxide (TiOx) as an electron collection electrode with the structure ITO/TiO(x)/[6,6]-phenyl C(61) butyric acid methyl ester (PCBM): regioregular poly(3-hexylthiophene) (P3HT)/poly(3,4-ethylenedioxylenethiophene):poly(4-styrene sulfonic acid)/Au (TiO(x) cell) was fabricated. Its complicated photovoltaic properties were investigated by photocurrent-voltage and alternating current impedance spectroscopy measurements. The TiO(x) cell required a significant amount of time (approximately 60 min) to reach its maximum power conversion efficiency (PCE) of 2.6%. To investigate the reason for this slow photoresponse, we investigated the influences of UV light and water molecules adsorbed on the TiO(x) layer. Surface treatment of the TiO(x) cell with water induced a rapid photoresponse and enhanced the performance, giving a PCE of 2.97%. However, the durability of the treated cell was considerably inferior that of the untreated cell because of UV-induced photodegradation. The cause of the rapid photoresponse of the treated cell was attributed to the formation of hydrogen bonds between adsorbed water molecules and carbonyl oxygen atoms in PCBM close to the TiO(x) surface. When the TiO(x) surface was positively charged by UV-induced holes, the carbonyl oxygen in PCBM close to the TiO(x) surface can quickly join to the TiO(x) surface, rapidly transporting photogenerated electrons from PCBM to TiO(x) in competition with the photocatalyzed degradation. The experimental results suggested that the slow photoresponse of the untreated TiO(x) cell was because the morphology of the photoactive organic layer changed gradually upon irradiation to improve the transport of photocarriers at the TiO(x)/PCBM:P3HT interface.