A heated DESI spray device provides improved resolution or control of analyte desorption at a target locus on a sample. Heating controls spot size and enhances resolution in an imaging mode without impairing signal level. Additionally or alternatively the heated DESI spray may control desorption kinetics of a target analyte or otherwise control analyte discrimination in detection mode. One embodiment of the DESI spray is heated by heating nebulizing gas that accompanies the electrosprayed solvent. Another embodiment heats a separate gas stream that transports or directs desorbed material to the ion aperture of an analysis instrument. Heating may reduce size of primary droplets, alter the impact dynamics or the energy delivered by the spray to the surface, reduce size of secondary droplets and/or assure desolvation, improve species selectivity or otherwise affect sampling and enhance the ion signal level.