Niobium pentoxide (Nb2O5) based thin films are predominantly used in optical filters, solar cells, electrochromic devices, sensors and microelectronic devices. The temperature-dependent thermophysical properties of Nb2O5 films are crucial for the performance and reliability of such devices. Within this work, for the first time, the thermal properties of sputter deposited Nb2O5 films are correlated with their structural properties at different length scales. Thermal measurements were carried out by time-domain thermoreflectance, yielding a thermal conductivity of 3.0±0.3 W/mK at 25 °C for crystalline Nb2O5 films, which decreases to 2.6±0.2 W/mK at 450 °C. In contrast, amorphous Nb2O5 films had a thermal conductivity of 2.2±0.2 W/mK below 275 °C. Above 275 °C, an abrupt increase in thermal conductivity up to a maximum value of 2.8±0.2 W/mK at 325 °C was recorded. The average and local structure are determined by in-situ high-temperature X-ray diffraction and in-situ high-temperature Raman spectroscopy, respectively. These characterization techniques together enable to cross-correlate structural and thermal properties of Nb2O5 thin films highlighting the observed peculiarity of the thermal conductivity. This substantial increase in thermal conductivity cannot be linked to any macroscopic phase change but rather to a local phase rearrangement near the crystallization temperature, evidenced by temperature-dependent Raman spectra analysis. This study serves as a guide to engineering future Nb2O5 based thin film devices and for their reliability optimization.