The fifth-generation atmospheric reanalysis of the European Center for Medium-Range Weather Forecasts (ERA5) is the latest reanalysis product. However, the reliability of ERA5 to capture extreme temperatures is still unclear over China. Hence, based on conventional meteorological station data, a new criterion (DISO) was used to validate the ERA5 capturing extreme temperature indices derived from the Expert Team on Climate Change Detection and Indices (ETCCDI) across the six subregions of China on different timescales. The conclusions are as follows: the original daily temperatures (mean temperature, maximum temperature, and minimum temperature) can be well reproduced by ERA5 reanalysis over China. ERA5 tends to exhibit more misdetection for the duration of extreme temperature events than extreme temperature intensity and frequency. In addition, ERA5 performed best in the summer and worst in the winter, respectively. The trend of absolute indices (e.g., TXx and TNx), percentile-based indices (e.g., TX90p, TX10p, TN90p, and TN10p), and duration indices (e.g., WSDI, CSDI, and GSL) can be captured by ERA5, but ERA5 failed to capture the tendency of the diurnal temperature range (DTR) over China. Spatially, ERA5 performs well in southeastern China. However, it remains challenging to accurately recreate the extreme temperature events in the Tibetan Plateau. The elevation difference between the station and ERA5 grid point contributes to the main bias of reanalysis temperatures. The accuracy of ERA5 decreases with the increase in elevation discrepancy.