The present study focuses on finding a correlation between the positron annihilation parameters of silicone rubber polydimethylsiloxane (PDMS) composites loaded with different conductive fillers and their swelling and electrical properties. Four types of conductive fillers have been used in this study, i.e., carbon black (CB), graphite (G), copper, and nickel powders. The investigated swelling parameters for PDMS composites such as the maximum degree of swelling Q_m%, the penetration rate, P, and consequently the diffusion coefficient, D, decreased with increasing the filler content due to the reduction of the size of free‐volume, which could be observed through a decrease of the probability of ortho‐positronium (o‐Ps) formation I₃, that has been measured by the positron annihilation spectroscopy (PALS). Accordingly, a positive correlation has been found of 76.78% and 61.1% between Q_m% and the o‐Ps lifetime τ₃, representing the size of free‐volume for the CB and G filled composites, respectively. It is worthwhile, mentioning that the CB filled composites exhibit relatively low values of P, D, and Q_m% as compared to the G filled composites due to the difference in the physical properties of the filler, particle size, surface area as well as the tendency of the filler particles to make aggregates. On the other hand, the variation of the diffusion coefficient with the relative fractional free‐volume F_r is found in good agreement with the Fujita's free‐volume theory. On the other hand, the electrical conductivity increases with increasing the conductive filler content. Positive temperature coefficient of conductivity (PTCC) behavior is detected, except for the composite containing 20 or 25 phr CB, which showed a metallic behavior. Besides, CB filled PDMS composites exhibit higher electrical conductivity as compared to the composites filled with the other three fillers. The electrical conductivity ln (σ) is positively correlated with the probability of free annihilation of positrons at interfaces I₂, thus suggesting an increase in the electron density with the filler content. The activation energy of conduction, E_a, decreases with the increase in the loading of conductive filler. Moreover, it was noticed that E_a varies with the filler type, the values of E_a increase as the particle size of the filler increases. Finally, a correlation between the free‐volume V_f, determined by PALS with the DC electrical conductivity ln(σ) is found to be in accordance with Miyamoto and Shibayma model. POLYM. COMPOS., 34:2105–2115, 2013. © 2013 Society of Plastics Engineers