Silicone rubbers have been widely employed in various fields such as electronics, electrical engineering, mobile communications, aerospace, and automotive industries. However, silicone rubbers are typically challenging to reprocess and degrade. Moreover, with the advancement of technology, higher demands have been placed on its thermal conductivity and dielectric properties. In this study, diglycidyl ether terminated polydimethylsiloxane was cured by 4,4′‐dithiodibutyric acid which contains dual dynamic covalent disulfide and ester bonds with triazobicyclodecene as the ester exchange catalyst to prepare silicone rubber vitrimers (SRVs) through a casting method. The SRVs demonstrated a relatively higher intrinsic thermal conductivity of 0.26 W/(m·K) compared to ∼0.20 W/(m·K) of conventional silicone rubber. Besides, the SRVs exhibited very low and stable dielectric constant and dielectric loss at both low and high frequencies (X‐band). The lowest dielectric constant and dielectric loss tangent at 10 GHz were 2.75 and 0.0639, respectively. Besides, the dual dynamic covalent bonds enabled the SRVs to have excellent reprocessability and fast degradability. Moreover, the SRVs revealed UV‐shielding capability, as the transmittance of the SRVs was 0% from 200 to 400 nm of UV light.This article is protected by copyright. All rights reserved