A plasma chemical vapor deposition method for forming a film on a substrate which is placed on one of a pair of electrodes oppositely arranged within the reaction chamber of a reactor. A plurality of power generators of different frequencies are applied to the electrodes to excite reactive gases introduced into the reaction chamber, whereby the reactive gases are transformed into a plasma and a desired film is formed on the substrate. Film with a small number of pinholes was formed at a relatively high deposition rate by combinations of power generator frequencies of, for example, 13.56 MHz and 1 MHz, 13.56 MHz and 50 KHz, and 5 MHz and 400 KHz.