We applied liquid-source vapor deposition (LVD), thermal CVD from the vapor of cyclopentasilane (CPS), to form amorphous silicon (a-Si) passivation films on crystalline Si (c-Si) wafers, and investigated the thermal stability of the films against postannealing. LVD a-Si passivation films showed a high initial effective minority carrier lifetime (τeff) of >300 µs and a higher thermal stability than a reference plasma-enhanced chemical-vapor-deposited (PECVD) sample. The high thermal stability of LVD a-Si passivation films may be attributed to the considerably high deposition temperature of the films at 360 °C or more. LVD a-Si passivation films were sufficiently stable also against air exposure and 1-sun light soaking. We also confirmed that the epitaxial growth of Si films does not occur on c-Si even at such high deposition temperatures, and LVD could realize the simultaneous deposition of a-Si films on both sides of a c-Si wafer.