Surface modified TiO2 materials are widely used in photocatalytic environmental purification processes. The employment of solution might exert a discernible influence on the catalyst. In this study, we incorporated tetrahydrofuran (THF) and pyrrolidine (PY) during the hydrolysis of titanium butoxide (TBOT) to modify the surface of TiO2, successfully synthesizing surface C-modified TiO2 (THF-TiO2) and surface CN-modified TiO2 (PY-TiO2) catalysts. The assistance of THF and PY not only reduced agglomeration, but also increased the specific surface area of both catalysts, leading to the exposure of more active sites in TiO2 during the photocatalytic degradation of toluene. When compared to the unsatisfactory degradation of toluene (80%) and CO2 mineralization efficiencies (40–45 %) observed using unmodified TiO2, the synthesized THF-50-TiO2 and PY-1-TiO2 microspheres demonstrated enhanced toluene degradation efficiency to 100 % and 99.8 %, respectively, and improved mineralization efficiencies to 76 % and 80 % after 120 min of ultraviolet irradiation. The experimental data and characterization results indicate that the surface-modified carbon species in THF-50-TiO2 facilitate the acceleration of electron-hole pair separation and suppress recombination. In contrast, partial nitrogen species introduced into the surface lattice of PY-1-TiO2 narrow its band gap and induce a visible light response. Overall, this study provides two methods to modify the surface of TiO2, which can be applied to prepare outstanding photocatalysts for possible application in the degradation of volatile organic compounds (VOCs) present in the air. Furthermore, it has been confirmed that solution have a significant impact on the catalyst.