Abstract: A multifunctional double-loaded core–shell hydrogel was developed for the stepwise degradation of organic pollutants using microorganisms and photocatalysts. The hydrogel core was coated with polyvinyl alcohol (PVA) and hydroxyethylcellulose (HEC) coated with yeast (YE) and the shell consisted of sodium alginate (SA) and calcium ions (Ca2+) loaded with titanium dioxide nanoparticles (TiO2 NPs). Scanning electron microscopy measurements revealed that the core–shell structure was clear and distinct, while the micrographs and fluorescent labeling photos proved the existence of YE in the core. The successful loading of TiO2 NPs in the shell was confirmed by X-ray diffraction analysis, while Fourier transform infrared and X-ray photoelectron spectroscopic recordings verified the development of intermolecular interactions in the core–shell structure. The applicability of the developed core–shell hydrogel was examined in the stepwise degradation of methylene blue (MB) dye using different YE and TiO2 NPs loadings. High TiO2 NPs shell loadings promoted the degradation of MB, which could reach 96.65%, whereas the MB degradation rate first increased and then decreased to 92.15% with increasing YE loadings. After 4 cycles of degradation, the degradation rate of MB dye still be 68.97%.The successful results of this study are expected to serve as a guide for the development of new degradation methods for the removal of various organic pollutants.