Physical　properties　of　phase　transition　materials　are　directly　linked　to　the　transformation　of　structural　moieties.　Here,　we　report　a　new　hydrogen-bonded　binary　crystal　of　cyclohexylaminium　chlorodifluoroacetate　(1),　consisting　of　two　distinct　types　of　the　anion-cationic　structural　moieties,　which　shows　an　order-disorder　phase　transition　around　153　K　(phase　transition　point,　Tc).　Thermal　analyses,　dielectric,　and　second-order　nonlinear　optical　(NLO)　measurements　solidly　confirm　the　symmetry　transformation　from　the　point　group　mmm　to　mm2.　It　is　noteworthy　that　1　exhibits　a　coexistence　of　switchable　dielectric　behaviors　and　bistable　NLO　effects.　In　detail,　it　is　NLO-active　below　Tc,　while　its　quadratic　NLO　effects　completely　disappear　above　Tc.　Such　a　change　reveals　the　bistable　feature　of　its　quadratic　NLO　properties.　Further,　variable-temperature　structure　analyses　reveal　that　the　emergence　of　NLO　effects　below　Tc　is　ascribed　to　partial　ordering　of　anions　and　small-angle　reorientation　of　cations.　This　mechanism　is　different　from　that　of　the　precedent　NLO-switching　materials,　which　affords　a　potential　avenue　to　design　new　electric-ordered　molecular　compounds　as　multifunctional　materials.　©　2017　American　Chemical　Society.