Photosynthesis is a highly efficient solar energy transformation process. Exploiting this natural phenomenon is one way to overcome the shortage in the Earth's fuel resources. This review summarizes the work carried out in the field of photobioreactor design via the immobilization of photosynthetically active matter within biologically inert matrices and the potential biotechnological applications of the obtained hybrid materials within the domain of solar energy to chemical energy transformation. The first part deals with the design of artificial photosynthetic reaction centers (RCs) by the encapsulation of pigments, proteins, and complexes. The action of thylakoids, chloroplasts, and whole plant cells, immobilized in biocompatible supports, in the conversion of CO into chemical energy, is also addressed. Finally, the latest advances in the exploitation of the bioactivity of photosynthetically active micro-organisms are explored in terms of the production of secondary metabolites and hydrogen.