Microbe-material hybrid systems which facilitate the solar-driven synthesis of high-value chemicals, harness the unique capabilities of microbes, maintaining the high-selectivity catalytic abilities, while concurrently incorporating exogenous materials to confer novel functionalities. The effective assembly of both components is essential for the overall functionality of microbe-material hybrid systems. Herein, we conducted a critical review of microbe-material hybrid systems for solar energy conversion focusing on the perspective of interface assembly strategies between microbes and materials, which are categorized into five types: cell uptake, intracellular synthesis, extracellular mineralization, electrostatic adsorption, and cell encapsulation. Moreover, this review elucidates the mechanisms by which microbe-material hybrid systems convert elementary substrates, such as carbon dioxide, nitrogen, and water, into high-value chemicals or materials for energy generation.