FDO’s wide boiling range and complex composition hinder controlled synthesis of high-performance mesophase pitch. Here, FDO was separated into light, middle, and heavy narrow fractions by vacuum distillation. Multi-scale characterization traced molecular evolution and mesophase development. The light fraction consists of three-ring aromatics with short alkyl side chains and shows the lowest reactivity, yielding limited condensation and poor stacking with isotropic regions and dispersed spheres. The middle fraction contains four-ring aromatics with moderately extended chains, exhibiting enhanced reactivity and undergoing nucleation, growth, coalescence, and disintegration of mesophase spheres. However, insufficient volatiles restrict shear orientation, forming a mosaic texture. The heavy fraction has four-ring aromatics with the longest alkyl chains and the lowest substitution degree, giving the highest reactivity. During thermal cracking, long chains release abundant radicals and volatiles; directional escape generates shear, promoting rapid growth and ordered alignment of aromatic lamellae. At 440 °C for 12 h, this fraction yields high-quality mesophase pitch with small-domain texture, a low softening point (295 °C), and high anisotropic content (98.8%). The pitch shows excellent spinnability, and derived carbon fibers (tensile strength ~1.45 GPa, modulus ~151 GPa) outperform a commercial reference processed under identical conditions. This study reveals molecular-level regulation of mesophase evolution by narrow fraction structures.