A hydrometallurgical route is proposed in this paper for the selective separation of zinc and manganese from spent alkaline batteries. The recycling route comprises the following steps: (1) batteries dismantling to separate the spent batteries dust from other components (iron scraps, plastic and paper), (2) grinding of the batteries dust to produce a black homogeneous powder, (3) leaching of the powder in two sequential steps, “neutral leaching with water” to separate potassium and produce a KOH solution, followed by an “acidic leaching with sulphuric acid” to remove zinc and manganese from the powder, and (4) selective precipitation of zinc and manganese using the KOH solution (pH around 11) produced in the neutral leaching step. For the acidic leaching step, two alternative routes have been investigated (selective leaching of zinc and total leaching) with regard to the following operational variables: temperature, time, sulphuric acid concentration, hydrogen peroxide concentration and solid/liquid ratio. The results obtained in this study have shown that the proposed route is technically simple, versatile and provides efficient separation of zinc and manganese.