Bismuth oxyhalide (Bi-O-X) is a group of layered semiconductors, which are promising candidates for photocatalysis due to their inherent internal electric field and adjustable band gap through composition and morphology control. Bismuth-rich Bi-OX has improved stability and advantageous band structure compared to those of Bi-O-X and hence has attracted an increasing amount of research interest. In this work, ultrathin nanotubes of Bi5O7I with a 5 nm diameter and a 1 nm wall are obtained through a hydrothermal method while the phase and morphology of the products are regulated by the pH values and polyvinylpyrrolidone (PVP) concentration of the reaction system, of which the products can be tuned from BiOI nanosheets to Bi5O7I nanobelts and ultrathin Bi5O7I nanotubes. PVP and pH control is important to the formation of the nanotubes as formation occurs via a PVP-guided oriented attachment from primary nanoparticles of Bi5O7I. The poorly crystalline and porous structure of the resultant bismuth-rich ultrathin nanotubes not only exposes more surface atoms but also exhibits a highly reduced conduction band minimum. The resultant band gap of 2.39 eV (as compared to 3.20 eV for the nanobelts) arises from the undercoordinated bismuth centers brought about by the rich oxygen vacancies in the nanotubes. The largely reduced band gap effectively enhances visible-light absorption, while the short charge-diffusion length of the nanotubes further reduces the charge-carrier loss in recombination.