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.

Complete ethanol oxidation reaction (EOR) in C1 pathway with 12 transferred electrons is highly desirable yet challenging in direct ethanol fuel cells. Herein, PtRh jagged nanowires synthesized via a simple wet‐chemical approach exhibit exceptional EOR mass activity of 1.63 A mgPt⁻¹ and specific activity of 4.07 mA cm⁻², 3.62‐fold and 4.28‐folds increments relative to Pt/C, respectively. High proportions of 69.33% and 73.42% of initial activity are also retained after chronoamperometric test (80 000 s) and 1500 consecutive potential cycles, respectively. More importantly, it is found that PtRh jagged nanowires possess superb anti‐CO poisoning capability. Combining X‐ray absorption spectroscopy, X‐ray photoelectron spectroscopy as well as density functional theory calculations unveil that the remarkable catalytic activity and CO tolerance stem from both the Rh‐induced electronic effect and geometric effect (manifested by shortened Pt─Pt bond length and shrinkage of lattice constants), which facilitates EOR catalysis in C1 pathway and improves reaction kinetics by reducing energy barriers of rate‐determining steps (such as *CO → *COOH). The C1 pathway efficiency of PtRh jagged nanowires is further verified by the high intensity of CO₂ relative to CH₃COOH/CH₃CHO in infrared reflection absorption spectroscopy.