A new synthetic approach to generate highly porous semiconductor networks that could be used for catalytic and solar cell applications is reported. Titanium dioxide networks were produced using a polymer gel templating procedure, resulting in a coral-like structure with a wall thickness of about 100-150 nm and pore sizes ranging from 100 nm to micrometers in diameter. Calcination results in the production of either the anatase or rutile crystal phases without carbon contamination from the starting polymer materials, with the individual titanium dioxide particles contacting neighbors, thereby forming a continuous network. The results obtained are of importance to various fields of research as the open "coral-like" network structure of the titanium dioxide allows high access of the titanium dioxide surface to the reaction medium.