A polymer nanoparticle network using single-chain nanoparticles (SCNPs) as cross-links is designed. The experimental and theoretical study shows that incorporating SCNPs in polymer networks leads to smaller mesh size, faster terminal relaxation time, and reduced fluctuation among cross-links, resulting in a significant increase in shear storage modulus, and enhancement in tensile stress. Notably, the reversible single-chain collapse of SCNPs under thermal stimulation enables the polymer network to undergo coherent changes between two topological states, thereby exhibiting reversible transformations between soft and stiff states. This approach and finding can effectively tailor the mechanical properties of polymer networks, potentially leading to the development of intelligent, responsive materials.