Photosynthetic energy conversion for high-energy chemicals generation is one of the most viable solutions to the quest for sustainable energy towards carbon neutrality. Microalgae are fascinating photosynthetic organisms, which can directly convert solar energy to chemical energy and electrical energy. However, microalgal photosynthetic energy has not yet been applicated at large scale, due to the limitation of their own characteristics. Researchers have been inspired to couple microalgae with synthetic materials via biomimetic assembly, and the resulting microalgae-material hybrids become more robust and even perform new functions. In the past decade, great progress has been made in microalgae-material hybrid, such as photosynthetic carbon dioxide fixation, photosynthetic hydrogen production, photoelectrochemical energy conversion, and even biochemical energy conversion for biomedical therapy. Microalgae-material hybrid offers opportunities to promote artificially enhanced photosynthesis research and synchronously inspires investigation of biotic-abiotic interface manipulation. This review summarizes current construction methods of microalgae-material hybrids and highlights their implication in energy and health. Moreover, we discuss the current problems and future challenges for microalgae-material hybrids and the outlook for their development and applications. This review will provide inspiration for rational design of microalgae-based semi-natural biohybrid and further promote the disciplinary fusion of material science and biological science.