The study of diffusion and permeation of methane, nitrogen, and helium in miscible blends of poly(styrene-stat-acrylonitrile) (PSAN) and poly (methyl methacrylate) (PMMA) at 35–140°C shows that permeation coefficients (P) of helium followed the linear logarithmic mixing rule. Positive deviations from the linear logarithmic mixing rule were observed for permeation and diffusion coefficients (D) of methane and nitrogen below the glass transition temperature (Tg). The deviations decreased with increasing temperature and disappeared above Tg. The experimental results were analyzed by free volume and activated state theories. The Arrnenius plots of log D or log P vs. the reciprocal of temperature exhibited discontinuities in the glass transition region for all gases and blend compositions. The discontinuities are caused by large thermal expansion coefficient differences between the rubbery and glassy states of PSAN and PMMA. The sorption of methane in 50/50 PSAN/PMMA has dual-mode characteristics below Tg.