This paper describes the fabrication of polyelectrolyte microspheres using porous manganese carbonate as a sacrificial template for entrapped photosensitizer (PS) drugs for photodynamic therapy application. These particles were used as templates for polyelectrolyte layer-by-layer assembly (Lbl) of two oppositely charged polyelectrolytes: poly(styrene sulfonate) and poly(allylamine hydrochloride). When the polyelectrolyte multilayer shell was built around the MnCO3 core by the Lbl protocol and the core was extracted with acid solution and EDTA, the resultant assembly consisted of hollow polyelectrolyte spheres. Chloroaluminum phthalocyanine was chosen as the model drug to load into the hollow spheres. All the spectroscopic results presented showed excellent photophysical parameters of the studied drug. The fabrication of polyelectrolyte hollow spheres can be used as an optimal medium for a variety of bioactive materials, which can also be encapsulated by the proposed method.