Under the background of global warming, climate extremes have become a crucial issue with distinct heterogeneity features in different regions. Hence, spatial–temporal changes in temperature and precipitation extremes in Guizhou Province were investigated utilizing daily maximums and minimums of temperature and daily precipitation data during 1960–2019 based on trend analysis. It was concluded that, firstly, all warm extremes but warm spell duration indicator (WSDI) are significantly enhanced, whereas for cold extremes, the monthly minimum value of daily minimum temperature (TNn) is significantly enhanced, while cool nights (TN10P), frost days (FD0), ice days (ID0), and cold spell duration indicator (CSDI) are significantly decreased. And all precipitation extremes but consecutive wet days (CWD) have no significant variational trend in Guizhou Province. Secondly, variational trends of temperature extremes are more prominent and robust in western Guizhou Province. Temperature and precipitation extremes show large differences from spring to winter. Thirdly, temperature extremes are closely correlated with strength, area, and the westernmost ridge point index of western Pacific subtropical high (WPSH), whereas precipitation extremes show no distinct correlation with WPSH. The WPSH has significantly strengthened and shifted westward in the past 60 years, leading to less total cloud cover and more downward solar wave flux reaching Earth’s surface, accordingly, exacerbating warm extremes and weakening cold extremes. These results will benefit understanding the heterogeneity of climate extremes at a regional scale.