Refractory organic matter (RfOM) is ubiquitous in aquatic environment and plays various roles in regulating the fate, transport, toxicity, and bioavailability of chemical species, such as metals, emerging organic contaminants, and nanomaterials. RfOM is mainly represented by humic acids (HA) as the acid insoluble fraction of organic matrix. Considering the complex and multicomponent characteristic of HA, a detailed study was designed to elucidate the fate of molecular size fractions (MSFrs) of humic under solar irradiation in the presence of polyaniline (PANI)-modified TiO2 composites. Humic acid as a consortium of diverse molecular size fractions with different tendencies towards oxidation requires further assessment by UV-vis and fluorescence spectroscopic parameters complementary to previous studies on the photocatalytic degradation of RfOM by using TiO2 and PANI-TiO2 composites. Absorbance-based removal efficiencies under initial and post-photocatalytic conditions showed a re-formation trend during photocatalysis in the presence of PANI and TiO2 where higher MSFrs were transformed to lower MSFrs that was apparent for < 3kDa fraction. Completely different profiles were observed for PT-41 and PT-81 indicating similar degradation pathways independent of PANI ratio in the composite. As confirmed by the investigated parameters, formation of both 450kDa and 220kDa MSFrs were evident under all conditions indicating in situ generation of higher MSFrs. The eligibility of coupled absorbance-fluorescence measurements to discern molecular size distribution of humic acid via oxidative degradation was also investigated. Excitation-emission matrix (EEM) contour plots emphasized the ratio dependency of PANI modification of TiO2 and revealed sample specific variations that were more pronounced in terms of the emergence of tyrosine- and tryptophan-like aromatic proteins.