Mesoporous TiO2 nanoparticles were synthesized at different temperatures (400–800 °C). The resulting mesoporous anatase–rutile TiO2 mixtures between 27 and 82% were found to have different structural properties (morphology, mesoporosity, crystallite phases, and sizes) affected through the calcination process. They were tested for the photocatalytic degradation of the herbicides imazapyr and phenol, compared with the nonporous TiO2 P-25. The present work is an extension of a previously published study discussing the influence of the rutile content on the photocatalytic performance of the nanocrystals, based on the modified first order kinetic model, where the degradation rate is a function of the specific surface area of the material. The apparent degradation rate using T-800 is 10-fold higher than in the case using TiO2 P-25. The material with the lowest anatase content (T-800) exhibits the highest photocatalytic activity in terms of initial reaction rate per unit surface area. It is considered that mixed-phase photocatalysts with rutile–anatase exhibit enhanced photoactivity with the increase of the rutile proportion.