The allotrope of carbon, biphenylene, was prepared experimentally recently [Fan et al., Science 372, 852–856 (2021)]. In this Letter, we perform first-principles simulation to understand the bonding nature and structure stability of the possible in-plane heterostructure built by graphene and biphenylene. We found that the graphene–biphenylene in-plane heterostructure only exhibits along the armchair direction, which is connected together by strong covalent bonds and energetically stable. Then, the non-equilibrium molecular dynamics calculations are used to explore the interfacial thermal properties of the graphene/biphenylene heterostructure. It is found that the graphene/biphenylene in-plane heterostructure possesses an excellent interfacial thermal conductance of 2.84 × 109 W·K−1·m−2 at room temperature. Importantly, the interfacial thermal conductance presents different temperature dependence under opposite heat flux direction. This anomalous temperature dependence results in increased thermal rectification ratio with temperature about 40% at 350 K. This work provides comprehensive insight into the graphene–biphenylene heterostructure and suggests a route for designing a thermal rectifier with high efficiency.