Polycrystalline diamond (PCD) was grown onto high-k dielectric passivated AlGaN/GaN-on-Si high electron mobility transistor (HEMT) structures, with film thicknesses ranging from 155 to 1000 nm. Transient thermoreflectance results were combined with device thermal simulations to investigate the heat spreading benefit of the diamond layer. The observed thermal conductivity (κDia) of PCD films is one-to-two orders of magnitude lower than that of bulk PCD and exhibits a strong layer thickness dependence, which is attributed to the grain size evolution. The films exhibit a weak temperature dependence of κDia in the measured 25–225 °C range. Device simulation using the experimental κDia and thermal boundary resistance values predicts at best a 15% reduction in peak temperature when the source-drain opening of a passivated AlGaN/GaN-on-Si HEMT is overgrown with PCD.