It is crucial for the efficiency of photocatalytic reactions how to separate the photo-excited electrons and holes and how to utilize them at interfaces. There are two main difficulties to make these possible; variations of defects and co-catalysts. Most of the metal oxide photocatalysts have shallow and deep trap states, whose structure is always controversial. It is hard to tell which state helps reaction or not. Various co-catalysts have been applied, but also it is difficult to tell the real effect; charge separation or the surface passivation. Here, we will show the method to distinguish the defect type from the electron dynamics by using the transient grating (TG) method, which has a high sensitivity at the interface. We prepared a film sample by heating a TiO2 paste on a glass substrate. The film was contacted with a reactant solution sandwiched by another glass and a spacer. The TG method is one of the time-resolved techniques, which measures the refractive index change at the interface after shining a pulse excitation light. We could distinguish three different routes for photo-excited electrons; bulk trap (<100 ns), surface trap (1-5 us), Ti trap (0.5 – 10 s). Only the surface trap showed reactivity with reactants on the solution side. Ti trap had a longer lifetime, which was only observed when the photoexcited holes were scavenged. This trap seems to affect the cycle of the photocatalyst. This method offers simultaneous measurements of different trap states, and gives an insight of which defects have an actual reactivity.