Although poly(4-vinylpyridine) is believed to have good gas permselectivity, the intrinsic gas permeation property is rarely reported in the literature. The objective of this work is to study the the intrinsic gas permeation property of poly(4-vinylpyridine) using a free-standing film. Because of its brittleness and strong adhesion with most solid surfaces, a free-standing poly(4-vinylpyridine) film was therefore prepared from casting on a liquid mercury surface. The permeation behavior of He, H-2, O-2, N-2, CH4, and CO2 through the film was tested over a pressure range of 252 to 800 cm Hg at 35 degrees C. The permeability and solubility decrease slightly with an increase in pressure, whereas the diffusivity increases as pressure increases. The pressure-dependent phenomenon can be explained using the partial immobilization model and the dual sorption model. An effective gas molecule diameter, which: is defined as the square root of the product of gas collision and kinetic diameters, was used to correlate the diffusivity and gas molecule size, and an empirical equation was derived. Solubility is also a strong function of gas physical properties such as critical temperature and Lennard-Jones force constant, which are the measures of gas condensability and molecule interaction, respectively. In general, higher solubility in: a polymer is obtained for gases with greater condensability and stronger interaction. Typical gas permeabilities of poly(4-vinylpyridine) measured at 619 cm Hg and 35 degrees C are: 12.36 (He), 12.64 (H-2), 3.31 (CO2), 0.84 (O-2), 0.14 (CH4), and 0.13 (N-2) barrers.