Nb-coated Cu superconducting radiofrequency (SRF) cavities are of interest as a possible alternative to bulk Nb cavities for particle accelerators due to the high thermal conductivity of Cu and its lower cost than Nb. Studying the thermal diffusion properties in Nb thin films on Cu is important for developing Nb-coated Cu SRF cavities. In the present study, the thermal diffusivity of 100‒800 nm Nb films on Cu is measured by time-domain thermoreflectance (TDTR). The thermal diffusivity is obtained from a curve fit of the TDTR signal to a one-dimensional Fourier heat diffusion model over a time extending from 25 to 985 ps after laser-surface interaction. The film was examined by atomic force microscopy and scanning electron microscopy. The grain size and thermal diffusivity increase with film thickness. The thermal diffusivity reaches a value similar to that reported for bulk Nb for the 400 and 800 nm films, for which the average grain size is 47 ± 13 nm and 68 ± 18 nm, respectively. TDTR measurement for the 400-nm film taken over the temperature range of 293 to 40 K showed that the thermal diffusivity increases as the temperature is reduced. The results indicate that grain boundaries reduce the thermal diffusivity of the Nb film and, therefore, must be considered in Nb-coated Cu SRF cavities.