TiO2/ACF composites were prepared by the electrochemical method with Titanium (IV) n-butoxide (TNB) electrolyte under different electrochemical operation time. The BET surface area for TiO2/ACF composites decrease with the increase of electrochemical operation time. There is a single crystal structure which is anatase in all of the samples from the data of XRD. The SEM micrphotographs of TiO2/ACF composites show that the TiO2 particles were well mixed with the ACF. There are O and P with strong C and Ti peaks in all samples from EDX results, and it also shows that a decrease of the C content with a increasing of Ti content with increasing of the electrochemical operation time in the over all composites. DSC cures show that the exothermic peak of all composites at 560oC represents the transformation heat of amorphous parts to anatase phase and the discontinuous grain growth of the transformed anatase particles. Finally, the excellent photoactivity of TiO2/ACF composites (especially, ACFT10) could be attributed that the decrease of concentration of MB can be concluded to be much faster for the adsorption by ACF than for photocatalytic decomposition by TiO2. Keywords : Titanium (IV) n-butoxide (TNB), Activated carbon fiber, BET, XRD, SEM, EDX, DSC, photoactivity