Mesoporous TiO2 photocatalysts were prepared in ethanol media by using relatively green, template free sol-gel technique. A mild hydrothermal treatment procedure was employed to tune the pore sizes of the materials. Comprehensive techniques that include powder X-ray diffraction, diffuse reflectance spectroscopy, specific surface area analysis, electron microscopy, FT-IR, TGA, and xi-potential measurements were used to characterize the titania materials. Porosity (pore size and pore volume) of the materials were found to be key factors for the variation in the rate of photocatalytic degradation of rhodamine B; in addition to specific surface area, and surface hydroxyl groups. An increase in porosity permits effective transport of the dye molecules resulting in an increase in the rate of the degradation in materials having larger pores. A detailed electrospray ionization-mass spectrometric (ESI-MS) study was carried out for selected materials to identify photodegraded intermediates and products formed during the degradation of rhodamine B. In addition, experiments were also carried out to understand the role of reactive oxygen species (ROS). In summary, this work provides a simple way to tune pore sizes without the use of any template and an insight into the influence of pore size for the photocatalytic degradation of rhodamine B.