In this article we present the first comparative study of the transient decay dynamics of photo-generated charges for the three polymorphs of TiO2. To our knowledge, this is the first such study of the brookite phase of TiO2 over timescales relevant to the kinetics of water splitting. We find that the behavior of brookite, both in the dynamics of relaxation of photo-generated charges and in energetic distribution, is similar to the anatase phase of TiO2. Moreover, links between the rate of recombination of charge carriers, their energetic distribution and the mode of transport are made in light of our findings and used to account for the differences in water splitting efficiency observed across the three polymorphs.