One of the possible ways to enhance photocatalytic activity is the use of photonic band gap (PBG) materials. Anodic titania photonic crystals (PhCs) are promising PBG structures, whose structure can be tuned easily by anodizing conditions. However, the effect of various doping approaches on the photocatalytic activity of anodic titania PhCs has never been studied before. Here anodic titania PhCs were synthesized by cycling anodizing of titanium with voltage versus charge density modulation followed by annealing at 450 °C in air. The PhCs were post-treated by electrochemical reduction in 0.1 M Na2SO4, annealing in H2/Ar mixture or NH3. The phase composition and structure of titania PhCs were studied by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy. Photocatalytic activity of PhCs in the degradation of the methylene blue dye decreases after electrochemical reduction and annealing in NH3, whereas the annealing in H2/Ar at 600 °C for 2 h leads to an increase in the degradation rate constant by 60%. •Cyclic anodizing is applied for the preparation of 1D titania photonic crystals (PhCs).•Amount of oxygen vacancies in TiO2 increases after annealing in H2/Ar and NH3.•Photocatalytic activity of PhCs is demonstrated for methylene blue (MB) degradation.•Photocatalytic activity of PhCs decreases after electroreduction or annealing in NH3.•Annealing in H2/Ar leads to a 60% increase in the rate constant of MB degradation.