SnSe is challenging to use in thermoelectric devices due to difficulties in simultaneously optimizing its thermoelectric and mechanical properties. Here, the authors show a unique solvothermal synthetic environmental design to fabricate super‐large and micro/nanoporous Sn0.965Se microplates by using CrCl3. Cl− ions to trigger Sn‐vacancy formation and optimize the hole concentration to ≈3 × 1019 cm−3, while the as‐formed Cr(OH)3 colloidal precipitations act as “templates” to achieve micro/nanoporous features, leading to low lattice thermal conductivity of ≈0.2 W m−1 K−1 in the as‐sintered polycrystal, contributing to a high ZT of ≈2.4 at 823 K and an average ZT of ≈1.1. Of particular note, the polycrystal exhibits high hardness (≈2.26 GPa) and compression strength (≈109 MPa), strengthened by grain refinement and vacancy‐induced lattice distortions and dislocations; while a single‐leg device provides a stable output power (>100 mW) and conversion efficiency of ≈10% by a temperature difference of 425 K, indicating great potential for applying to practical thermoelectric devices. A solvothermal synthetic environmental design to fabricate super‐large and micro/nanoporous Sn0.965Se microplates using CrCl3 is employed, and the mechanically robust polycrystals sintered from these microplates exhibit a high ZT of ≈2.4 at 823 K and an average ZT of ≈1.1, leading to a conversion efficiency of ≈10% by a temperature difference of 425 K in the single‐leg device.