ZnAl layered double hydroxides (LDHs) were prepared by urea hydrolysis-based coprecipitation for removing phosphate from aqueous solutions. The chemical formula of the product was determined as Zn5.54Al3.02(OH)8.73(CO3)0.57Cl5.66·7.84H2O. Chloride ion was the major interlayer anion of the ZnAl LDHs. Adsorption of phosphate onto the ZnAl sorbent over the entire study period was not in close agreement with pseudo-first-order or pseudo-second-order models. The adsorption can be divided into two steps. A fast adsorption was observed during the first 10 h with a marked increase in the concentration of Cl− in the bulk solution. This indicated that the adsorption of phosphate was largely attributed to the ion exchange between phosphate and the interlayer Cl−. A second fast adsorption of phosphate occurred after 10 h. During this period, the pH increased slowly, whereas the Cl− concentration was stable. The uptake of phosphate was likely attributed to OH−–H2PO4−/HPO42− ion exchange as well as surface adsorption/complexation. Acidic conditions favored adsorption of phosphate by ZnAl LDHs, which is consistent with the pH increases during the adsorption. Coexisting anions, e.g., SO42− and CO32−, are competitive ions for the adsorption of phosphate. The results verify the contribution of ion exchange and surface adsorption/complexation in the removal of phosphate by ZnAl LDHs.