The strong interest in macroscopic graphene and/or carbon nanotube (CNT) fiber has highlighted that anisotropic nanostructured materials are ideal components for fabricating fiber assemblies. Prospectively, employing two-dimensional (2D) crystals or nanosheets of functionality-rich transition metal oxides would notably enrich the general knowledge for desirable fiber constructions and more importantly would greatly broaden the scope of functionalities. However, the fibers obtained up to now have been limited to carbon-related materials, while those made of 2D crystals of metal oxides have not been achieved, probably due to the intrinsically low mechanical stiffness of a molecular sheet of metal oxides, which is only few hundredths of that for graphene. Here, using 2D titania sheets as an illustrating example, we present the first successful fabrication of macroscopic fiber of metal oxides composed of highly aligned stacking sheets with enhanced sheet-to-sheet binding interactions. Regardless of the intrinsically weak Ti-O bond in molecular titania sheets, the optimal fiber manifested mechanical performance comparable to that documented for graphene or CNTs. This work provided important hints for devising optimized architecture in macroscopic assemblies, and the rich functionalities of titania promises fibers with limitless promise for a wealth of innovative applications.