Solidification/stabilization (S/S) of acid waste using Ordinary Portland Cement (OPC) is widely implemented, but, due to the impact on climate change, alternative methods are being investigated. In this work, first, the feasibility of using coal fly-ash/clay-based geopolymers for the S/S of Zn plant residues (ZPR), Cadmium Sponge (CS), and Anode Mud (AM) is proposed as a treatment prior to disposal in landfills. Different variables, such as the type of processing, molding (as-received waste), and pressing (dried waste), and activators, a commercial and an alternative residual sodium carbonate, have been studied. The technical and environmental assessments of the S/S process by means of compressive strength and the leaching of critical pollutants have been monitored. Immobilization efficiencies of Cd and Zn higher than 99% have been obtained by dosing 50% of the acid waste, 6 M NaOH solution (20 min contact time), cured at 75 °C (48 h) and at room temperature (28 days), achieving in the leachates pH values of 7 to 10 and [Cd] and [Zn] < 1 and 2.5 mg/kg, respectively. However, alkaline activation increases As leaching, mainly associated with the clay. Secondly, removing clay from the geopolymer formulation, the optimization of geopolymer parameters, acid waste/geopolymer ratio, liquid/solid ratio, and NaOH molar concentration enables obtaining a significant reduction in the release of As and Cd, and Zn is kept at acceptable values that meet the non-hazardous waste landfill disposal limits for the S/S of both acid wastes.