This paper presents an analysis of the relationship between land surface temperatures (LST) and screen‐level air temperatures (T2m) using in situ observations from 19 Atmospheric Radiation Measurement (ARM) deployments located in a range of geographical regimes. The diurnal cycle is resolved using 1 min observations: a particular focus of the study is on the relationship between daily extremes of LST (LSTmax, LSTmin) and T2m (Tmax, Tmin). Temperature differences are analyzed with respect to cloud, wind speed, and snow cover. Under cloud‐free, low wind speed conditions, daytime LST is often several degrees Celsius (°C) higher than T2m at low‐to‐middle latitudes and at high latitudes during the summer months. In contrast, LST and T2m are often close (e.g., within 2°C) under cloudy and/or moderate‐to‐high wind speed conditions or when solar insolation is low or absent. LSTmin and Tmin are generally well correlated (r > 0.8, often r > 0.9), while seasonal correlations between LSTmax and Tmax are weaker (r > 0.6, often r > 0.8). At high latitudes, LST and T2m are well coupled in spring/autumn/winter; the relationship between LST and T2m tends to weaken with decreasing latitude. The timing of daily extremes is also investigated and it is found that LSTmin and Tmin typically occur close to sunrise, with Tmin occurring slightly after LSTmin. LSTmax occurs close to solar noon, with Tmax typically occurring 1–3 hours later. This study will inform temperature data users on differences between LST and T2m and aid development of methods to estimate T2m using satellite LSTs.