An open-framework chalcogenidoantimonate, namely, [CH3NH3]4Ga4SbS9S0.28O0.72H (1), has been solvothermally synthesized and structurally characterized. Interestingly, 1 showed Ni2+ ion-exchange properties and wide pH resistance, with a maximum exchange capacity of 76.9 mg/g. To the best of our knowledge, this is the first example of amine-directed three-dimensional (3D) heterometallic chalcogenidometalates for the highly selective Ni2+ ion capture with the high distribution coefficient (Kd = 1.65 × 105 mL/g).