High-frequency plasma-enhanced chemical vapor deposition (HF-PECVD) is a widely applicable method of deposition over a large area at a high rate for fabricating silicon thin-film solar cells. This investigation presents the properties of hydrogenated amorphous silicon (a-Si:H) films and the preparation of highly-efficient p–i–n solar cells using an RF (27.1 MHz) excitation frequency. The influence of the power (10–40 W) and pressure (20–50 Pa) used during the deposition of absorber layers in p–i–n solar cells on the properties and mechanism of growth of the a-Si:H thin films and the solar cells is studied. The a-Si:H thin films prepared under various deposition conditions have widely varying deposition rates, optical-electronic properties and microstructures. When the deposition parameters were optimized, amorphous silicon-based thin-film silicon solar cells with efficiency of 7.6% were fabricated by HF-PECVD. These results are very encouraging for the future fabrication of highly-efficient thin-film solar cells by HF-PECVD.