This letter reports effective passivation of crystalline silicon (c-Si) surfaces by thermal atomic layer deposited tantalum oxide (Ta2O5) underneath plasma enhanced chemical vapour deposited silicon nitride (SiNx). Cross-sectional transmission electron microscopy imaging shows an approximately 2 nm thick interfacial layer between Ta2O5 and c-Si. Surface recombination velocities as low as 5.0 cm/s and 3.2 cm/s are attained on p-type 0.8 Ω·cm and n-type 1.0 Ω·cm c-Si wafers, respectively. Recombination current densities of 25 fA/cm2 and 68 fA/cm2 are measured on 150 Ω/sq boron-diffused p+ and 120 Ω/sq phosphorus-diffused n+ c-Si, respectively. Capacitance–voltage measurements reveal a negative fixed insulator charge density of −1.8 × 1012 cm−2 for the Ta2O5 film and −1.0 × 1012 cm−2 for the Ta2O5/SiNx stack. The Ta2O5/SiNx stack is demonstrated to be an excellent candidate for surface passivation of high efficiency silicon solar cells.