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The first paper describing a series of systematic investigations of the chemical shifts in Auger electron spectra from various free molecules is presented. Excitation is performed by means of a fine focus electron beam. The Auger electrons are retarded in a four component lens system and recorded at high resolution in a new multidetector system placed in the focal plane of the ESCA instrument. A calibration procedure against the KL₂L₃ Auger electron line of Ne is described. The first study concerns Auger electron line shifts for sulfur in some small molecules and the results are compared to the corresponding chemical shifts in the core photoelectron spectra. A formalism based on a transition potential model is briefly presented which takes account of the relaxation energies involved in Auger transitions as well as in single photoionization.