High quality surface passivation has gained a significant importance in photovoltaic industry for fabricating low cost and high efficiency solar cells using thinner and lower cost wafers. The passivation property of spin coated Al2O3 films with a thickness of about 50 nm on p-type Cz-Si wafers has been investigated as a function of annealing temperatures. An effective surface recombination velocity of 55 cm/s was obtained for the films annealed at 500 °C. The chemical and field effect passivation was analyzed by C-V measurements. A high density of negative fixed charges (Qf) in the order of 9 x 10(11) cm(-2) was detected in Al2O3 films and its impact on the level of surface passivation was demonstrated experimentally. The C-V curves show density of the interface state (Dit) of 1 x 10(12) eV(-1)cm(-2) at annealing temperature of 500 °C. During annealing, a thin interfacial SiOx is formed, and this interfacial layer is supposed to play a vital role in the origin of negative QF and Dit. The homogeneous SiOx interlayer result in higher passivation performance due to both the increase of negative Qf and the decrease of Dit.