Influence mechanism of side group types on the macroscopic electrical properties of silicone rubber (SiR) are analyzed based on the experimental comparison and the molecular simulation. The insulation properties of SiR with different side group types (vinyl, phenyl, and trifluoropropyl), as well as binary compound SiR (vinyl/phenyl and vinyl/trifluoropropyl) are compared and studied experimentally. Further, the effect of side groups on the movement of the molecular chain is analyzed by calculating the free volume, the mean square displacement (MSD), and the end distances. Then the mechanism of its influence on the macroscopic properties of SiR was studied. The experimental results indicated that the resistance and breakdown performance of the phenyl SiR surpasses both vinyl SiR and fluorosilicone rubber owing to the conjugated structure of benzene ring, which has a high electron affinity and reduces free charges and carrier migration rate. Besides, when 10wt% phenyl SiR was mixed into vinyl SiR, the resistivity increased by one order of magnitude, and the breakdown field strength increased by about 8%. In the aspect of dielectric properties, the fluorosilicone rubber is more qualified than the vinyl SiR and the phenyl SiR due to the addition of trifluoropropyl as a polar group to the non-polar dielectric SiR to boost its dielectric constant and dielectric loss. The molecular simulation results indicated that the SiR containing phenyl has a tiny free volume and weak molecular chain movement, the fluorosilicone rubber has the strongest molecular chain movement. The work has important guiding significance for improving and modifying SiR in power equipment.