Chemical vapor deposition (CVD) was firstly used to simultaneously codope fluorine and boron into TiO 2 nanotubes anodized Ti in C 2 H 2 O 4 ·2H 2 O+NH 4 F electrolyte. F–B-codoping was successfully carried out by annealing the anodized TiO 2 nanotubes through CVD, as evidenced from XPS analysis. SEM images showed that the higher the annealing temperature, the greater structure damage of F–B-codoped sample. XRD results confirmed that annealing temperature had an influence on the phase structure and boron and fluorine impurities could retard anatase–rutile phase transition. F–B-codoped samples displayed remarkably strong absorption in both UV and visible range. Under visible-light irradiation, F–B-codoped samples showed the higher I ph and catalytic activity in methyl orange photoelectrodegradation than F-doped sample and B-doped sample. This showed a convincing evidence of F–B-codoping of TiO 2 had an obvious synergistic effect on the enhancement of photocurrents and photoelectrocatalytic activity.