Carbon/TiO2 composite nanotubes were fabricated via a very simple electrospinning process and their dual functionalities of adsorptivity and photocatalytic activity were evaluated using Rhodamine B (RhB) as a model organic pollutant. A poly(vinyl alcohol) (PVA) aqueous solution was directly electrospun into a coagulation bath containing titanium (IV) tetraisopropoxide (TTIP) solution so that PVA-core/TiO2-shell composite nanofibers were formed through the in situ sol-gel reaction of TTIP. The carbon/TiO2 composite nanotubes were then fabricated by heat treatment of composite nanofibers under nitrogen atmosphere. By using several characterization methods, we confirmed that the resultant nanotubes consisted of anatase TiO2 nanocrystallites embedded in a carbonaceous matrix. The prepared nanotubes exhibited fast adsorption of RhB with high capacity compared with a commercial porous carbon, and they also showed the photocatalytic decomposition activity for the dye molecules under UV irradiation comparable to the degradation by P-25 and ST-01 (commercial TiO2). Finally, the carbon/TiO2 composite nanotubes exhibited several cycle performances of adsorption-photodegradation for RhB. This indicates that the composite nanotubes can adsorb and photodecompose organic pollutants repeatedly without additional activating processes.