The constituents of coal tar pitch (CTP) significantly impact the wettability of calcined coke (CC) and the performance of prebaked anodes (PA) used in aluminum electrolysis. However, balancing wettability and carbon residue within CTP remains a central challenge in material applications. In addition, limited pore permeability and structural stability in these composites hinder the effective utilization of PA. Enhancing CTP fluidity is crucial for overcoming these challenges. In this work, a novel method was developed to modify CTP utilizing various coal tar fractions, enabling controlled modulation of CTP composition and wettability. Incorporating different fractions allowed for substantial control over interfacial bonding and pore structure. The chemical composition, functional groups, and elemental content of the CTP were analyzed via X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and proton nuclear magnetic resonance (1H NMR). Subsequently, systematic comparisons of PA materials produced from different CTP formulations demonstrated improved wettability and enhanced mechanical properties. Moreover, DFT calculations were performed to compare the adsorption energies of small molecules from different coal tar fractions with coke, reflecting the interaction strength between the molecules and the solid surface. Using micro-computed tomography (μ-CT), the refined pore structure was examined, resulting in a PA composite with an optimized balance of high strength and toughness.