The structure and performance advantages of microstructured optical fibers (MOFs) have aroused an immense interest from researchers both locally and internationally, and the MOF emerges as a hot spot in the field of optoelectronics. Currently, according to the structure, MOF can either be solid-core or hollow-core. With respect to the transmission mechanism, they can be categorized as total internal reflection MOF, photonic bandgap MOF, and anti-resonant MOF. The important applications of MOF can be found in laser technology, optical sensing technology, optical communication technology, optoelectronic integration, and optical fiber devices. This paper conducts a review on the development history of MOF, presents a comprehensive analysis and summary of their various types, transmission mechanism, design, and fabrication, and provides a reference for exploring new research directions and applications of MOF in the future.