Polymerization-induced colloid aggregation is used to synthesize spheres of narrow size distribution which are porous aggregates of ZrO2 colloids. Variation of the reaction pH has been investigated to determine the optimum rate of polymerization of the urea-formaldehyde resin. At the optimum rate, a colloid packing structure is formed where a balance of high porosity and high strength of the aggregates is achieved. This optimum coincides with the maximum yield of the ∼5 μm sintered (polymer-free) particles. Particles synthesized at pH values below the optimum are mechanically weak; some are hollow spheres. Variation of the pore structure, and thus colloid packing structure, is elucidated by nitrogen adsorption and apparent density measurements. Differences on either side of the optimum pH are related to the efficiency of polymer-bridge formation between colloids.