The photoexcited electrons transfer dynamics of the CdS quantum dots (QDs) deposited in TiO2 nanowire array films are studied using surface photovoltage (SPV) and transient photovoltage (TPV) techniques. By comparing the SPV results with different thicknesses of QDs layers, we can separate the dynamic characteristics of photoexcited electrons injection and trapping. It is found that the TPV signals of photoexcited electrons trapped in the CdS QDs occur at timescales of about 2 × 10−8 s, which is faster than that of the photoexcited electrons injected from CdS into TiO2. More than 90 nm of the thickness of the CdS QDs layer will seriously affect the photoexcited electrons transfer and injection.