An improved optical design for nanosecond diffuse reflectance (DR) spectroscopy is presented. The in-situ analysis of the electron back-reaction and dye regeneration processes in efficient opaque dye-sensitized solar cell devices (DSCs) was scrutinized for the first time using nanosecond DR spectroscopy. The efficient DSC device is based on an opaque TiO2 double-layer film comprising 400 nm light-scattering particles and 20 nm optically transparent particles. Transmission-based laser techniques are not suitable for studying these or other devices by using the opaque morphologies of TiO2 films. However, time-resolved DR flash photolysis enables the exploration of photophysical processes in a broad variety of opaque or highly light-absorbing and light-scattering materials. We experimentally verified the three important components of DR-based spectroscopy: optical configuration, sample condition, and theoretical quantitative optical models. The large optical angle for diffusive light enables efficient light collection and measurement at a relatively low power. We tested the steady-state and time-resolved concentration dependence of the Kubelka−Munk theory for the quantitative analysis of time-resolved results and observed that the dynamics of electron back-reactions are strongly affected by the morphological parameters of the TiO2 films. With a lifetime of 50 μs, the kinetics of electron back-recombination in the device’s photoanode, which is manufactured with 400 nm TiO2 particles and 20 nm TiO2 particles, are 2 orders of magnitude faster than what has been reported to date for 20 nm particles (1 ms). In contrast to electron back-recombination, the dye regeneration process is not influenced by the TiO2 film morphology.