Many methods have been proposed for retrieving surface fluxes from one single measurement of surface temperature performed in the early afternoon, typically 14:00 LST. We analyse the interest of mid morning (10:00 LST) acquisition of surface temperature with the same scope of deriving fluxes. An analysis of a large experimental data set shows that the differences between surface and air (at a 2 m height) temperatures around 10:00 and 14:00 LST are comparable. Simulations performed with two different soil/plant/atmosphere models confirm the close relationship existing between Ts‐Ta at 10:00 and 14:00 LST. Sensitivity tests show that this relationship remains rather insensitive to the roughness length and the water status of the vegetation canopy, and does not depend on seasonality. The possible differences between aerodynamic and brightness surface temperatures are discussed: they may explain small discrepancies between results derived from measured or simulated data. Finally, the surface temperature at 10:00 LST seems as well suited for flux estimation purposes as the early afternoon one. In this case, the need of a precise maintenance of the overpass time is pointed out, as well as the necessity of performing corrections of local time along scan lines for polar orbiting satellites. Moreover the 10:00 LST acquisition time offers a greater probability of cloudfree conditions, which is a favourable element for studies requiring a continuous monitoring of surface conditions.