Owing to the rapid development of the latest micro-electronic devices, polymer composite materials that combine high thermal conductivity and low permittivity have aroused the interest of researchers. However, it is a huge challenge to balance the above parameters. In this work, hexagonal boron nitride (h-BN) powder was ultrasonically exfoliated to obtain alkylated boron nitride nanosheets (Alkyl-BNNS). Then, a series of polyimide (PI) composites were synthesized with different amounts of Alkyl-BNNS. Attributed to more robust interfacial non-covalent interactions between Alkyl-BNNS and polymer chains to inhibit interfacial polarization, Alkyl-BNNS can be scattered well in PI substrate. Thus, the obtained PI composite behaved a high thermal conductivity of 6.21 W/(mK) and a low dielectric constant (3.23) under the load of 20 wt%. Besides, Alkyl-BNNS/PI composites have efficient thermal management capability, low water absorption, favorable electrical resistance, and prominent tensile strength. Importantly, these composite films are expected to be excellent candidates in the field of microelectronics.