Nanometer-size holes in plasma-polymerized thin films were characterized by variable-energy positron lifetime spectroscopy for the first time. Hexamethyldisiloxane (HMDSiO) was plasma-polymerized at different discharge powers (30-105 W) and monomer pressures (1.0-4.9 Pa). The positron lifetime spectra of deposited films were collected at positron energies of 1 and 5 keV. All films showed a well-defined long-lived component due to pick-off annihilation of ortho-positronium (o-Ps). The o-Ps lifetime tau(3), reflecting the average size of free-volume holes in the film, increased with an increasing ratio of plasma discharge power, W, and monomer flow rate, F. Based on the empirical relationship between the o-Ps lifetime and the cavity radius, hole volumes were estimated to be 0.19-0.36 nm(3). We also found that the o-Ps intensity, I-3, depends strongly on the same parameter, W/F. Comparison with infrared (IR) absorption spectroscopy data showed that Ps formation is suppressed in films with fewer organic bonds and higher disorder, i.e., those increasingly inorganic in nature.