Artificial defect engineering in transition metal oxides is of important terms for numerous applications. In the present work, we proposed an in-situ gas reduction strategy to introduce ordered defects into titanium niobium oxide embedding on vapor grew carbon fibers (Ti₂Nb₁₀O_29–x@VGCFs). High-resolution transmission electron microscopy (HRTEM) and fast Fourier transform (FFT) simulation indicate that the ordered oxygen defects locate at interval layers, which leads to a new superstructure in Ti₂Nb₁₀O₂₉. The ordered defects could provide extra active sites for lithium-ion storage and modulate ionic migration, resulting an enhanced pseudocapacitive performance. In addition, the excellent structural stability of the superstructure was proved by in-situ HRTEM under a harsh electrochemical process. Our work provides a directly observation of orderly defective superstructure in transition metal oxide, and its functionality on electrochemistry was revealed.