Soft polymer gels encounter difficulties in meeting the demanding requirements of real-life applications due to the long-standing challenge to reproduce the excellent mechanical properties and multifunctionalities observed in natural soft tissues. Here, we proposed a freeze casting assisted solution substitution (FASS) strategy for hierarchically structured organo-hydrogel with an all-around performance, including record-breaking mechanical performances, superior long-term stability and tolerance to extreme conditions, together with excellent electrical conductivity and sensing capability. The underlying synergistic multi-scale reinforcement mechanisms are also validated. Hence, our works formulate a model design applicable to various polymer gels to expand their applications in flexible electronics, bionic sensors and soft robotics.