Effectively contacted multiwalled carbon nanotube (MWCNT)–titanium dioxide nanocomposites and phosphate-functionalized MWCNT–TiO2 composites have been successfully synthesized by simple one-pot phase-separated hydrolysis–solvothermal processes. The key to this synthetic strategy is to disperse MWCNTs uniformly in Ti(OBu)4 in advance and then to put them into the toluene organic phase. The as-prepared nanocomposites between TiO2 and the correct amount of MWCNT exhibits higher activity in the photocatalytic degradation of rhodamine B than that with the resulting TiO2, although the activity in the photocatalytic degradation of gas-phase aldehyde and liquid-phase phenol is lower. Interestingly, the functionalization of MWCNTs with an appropriate amount of phosphoric acids prior to the synthesis could greatly improve the activity of the MWCNT–TiO2 nanocomposites for the degradation of aldehyde and phenol, even superior to that of commercial P25 TiO2. Based on the measurements of atmosphere-controlled surface photovoltage spectra and O2 temperature-programmed desorption, it is suggested that MWCNTs are favorable to increase rhodamine B adsorption on the composite to promote the photosensitization oxidation reactions, whereas it is unfavorable for the adsorption of O2 and responsible for the low photocatalytic activity for the degradation of colorless pollutants. Phosphate functionalization greatly enhances the amount of O2 adsorbed on the MWCNT, which leads to significant charge separation, and thus, to significant photoactivity for the degradation of colored and colorless pollutants of the nanocomposites.