Highly oriented and self-ordered titanium-niobium-iron mixed oxide nanotubes were synthesized by anodizing Ti10NbxFe alloys in ethylene glycol electrolytes containing NH4F and water at 20 °C. The nanostructure morphologies were found to depend closely on the nature of the alloy substrates. The results demonstrate the possibility of growing mixed oxide nanotubes possessing several-micrometer-thick layers by a simple and straightforward electrochemical route. The methylene blue degradation rate of fabricated Ti-Nb-Fe-O nanotubes increased by 33% compared to TiO2 nanotubes and TiO2 nanoparticle films under solar irradiation. The combination of the gully-like morphology and the rich defects introduced by Nb and Fe co-doping in Ti-Nb-Fe-O mixed nanotube oxides was demonstrated to be beneficial for enhanced photocatalytic degradation performance. Ti-Nb-Fe-O nanotubes can achieve effective photodegradation without secondary pollution with more reusability than powder photocatalysts.