Silicone‐based elastomers are promising materials for future dielectric elastomer actuators. To ensure optimum performance and the long‐term reliability of the actuators, it is essential to gain a fundamental understanding of the correlation between the elastomer's network structure and the mechanical and electrical responses of the material. For this purpose, mechanical and electrical tests are performed on a series of silicone elastomer films with different crosslinking densities, which are prepared by changing the stoichiometric imbalance of the network. It is determined that higher cross‐linking density leads to a higher elastic modulus and a longer fatigue lifetime, whereas reduced permittivity is observed because of lower chain mobility. Dielectric breakdown strength is also observed to increase in line with increasing cross‐linking density, and the variations in relation to the measured elastic modulus and permittivity agree well with the Stark–Garton model based on electromechanical instability.