Thermal boundary conductance is becoming increasingly important in microelectronic device design and thermal management. Although there has been much success in predicting and modeling thermal boundary conductance at low temperatures, the current models applied at temperatures more common in device operation are not adequate due to our current limited understanding of phonon transport channels. In this study, the scattering processes across Cr∕Si, Al∕Al2O3, Pt∕Al2O3, and Pt∕AlN interfaces were examined by transient thermoreflectance testing at high temperatures. At high temperatures, traditional models predict the thermal boundary conductance to be relatively constant in these systems due to assumptions about phonon elastic scattering. Experiments, however, show an increase in the conductance indicating inelastic phonon processes. Previous molecular dynamic simulations of simple interfaces indicate the presence of inelastic scattering, which increases interfacial transport linearly with temperature. The trends predicted computationally are similar to those found during experimental testing, exposing the role of multiple-phonon processes in thermal boundary conductance at high temperatures.