The long‐standing pursuit of a synthetic equivalent to tissue cartilage has sprouted significant new activities in strategies for new material synthesis, among them a noticeable one being the double‐network hydrogels (DN‐gels) scheme. DN‐gels were prepared from the combination of an anionic polyelectrolyte network and a lightly crosslinked neutral polymer. These hydrogels exhibit an intriguing combination of properties intrinsic to natural cartilage: a low surface friction coefficient and a fracture toughness much higher than either of the constituent materials. The reinforcement of a hard, brittle polymer gel with a soft, viscoelastic neutral polymer is counter‐intuitive. Based on our recent results from neutron scattering measurements, we proposed a deformation mechanism where the molecular association between these two polymers plays a pivotal role. In this work, we further evaluate the proposed mechanism by performing mechanical measurements on DN‐gel samples with different polyelectrolyte network structure. The experimental results provide qualitative support for the proposed deformation mechanism.