Nanostructured zinc sulfide can provide unique photonic, electronic, and catalytic properties that are of interest for applications ranging from bioimaging to photocatalysis. Here we report an easily controllable continuous method to produce porous and hollow ZnS nano- and microspheres. We used poly(ethylene glycol) methyl ether (PEG), polyvinylpyrrolidone (PVP), ethylene oxide/propylene oxide block copolymer (Pluronic F-38), and cetyltrimethylammonium bromide (CTAB) as templates to synthesize ZnS nano- and microspheres with controlled internal morphology in a spray pyrolysis process, starting from an aqueous solution of chemical precursors and templating agents. Spherical particles were produced by droplet-to-particle conversion of droplets. Zinc acetate and thiourea, used here as precursors for ZnS, react in solution to form bis-thiourea zinc acetate (BTZA), which precipitates with the evaporation of solvent. Upon further heating, BTZA decomposes to yield ZnS. During solvent evaporation, PEG and Pluronic precipitate after BTZA, driving formation of a shell of ZnS and a hollow core. In contrast, PVP and CTAB interact strongly with BTZA and ZnS, such that the PVP and ZnS remain intermixed. After evaporation of solvent, the templating agents can be pyrolyzed at high temperature to leave behind porous or hollow ZnS microspheres composed of many much smaller nanocrystals.