Supramolecular polymer networks (SPNs) have attracted much research attention due to their good performance in the preparation of adaptive materials. Controlling the distribution of supramolecular interactions in the networks is a good strategy to tune the properties of SPNs, but corresponding study is still rare. Herein, we construct two triblock copolymers in ABA and BAB forms to control the supramolecular interaction concentrated in A block, leading to two SPNs with divergent mechanical performances. In specific, the SPN‐1formed by ABA triblock copolymer displays a slightly and densely distributed hard domain and a compact network, resulting in a decent toughness. While the SPN‐2composed of BAB triblock copolymer is rigid and less elastic, whose microphase‐separatedstructures are more obvious, making the network difficult to withstand larger strains. These findings are conducive to deepening the understanding of SPNs and would promote the development of supramolecular block copolymers with emergent functions and applications.