Abstract: Thermotropic liquid crystalline polyester (TLCP), characterized by their unique rigid rod-like molecular structures, combine exceptional properties such as high heat resistance, high modulus, and low dielectric constants, earning them the title of “super engineering plastics of the 21st century”. The optimization of their comprehensive performance depends on the synergy between molecular intrinsic structure and aggregated state structure: the former involves molecular design of mesogenic units to precisely control molecular rigidity-flexibility and alignment tendencies at the chemical level, while the latter relies on external field induction to achieve controllable preparation of microscale ordered structures and orientation states at the physical level. Focusing on TCLP systems, this review systematically summarizes strategies for regulating chain conformation and intermolecular interactions through molecular design, explores the evolution mechanisms of aggregated state structures and their regulatory effects on macroscopic properties, and provides an outlook on establishing polymerization reaction kinetic models for the precise construction of multi-level structures.