In this work, the first enantioseparation in a SF-SMB unit, i.e., a simulated moving bed (SMB) operated under supercritical conditions, is reported. Complete separation of the two enantiomers of tetralol was achieved both in the pressure-gradient mode (where a pressure gradient is imposed along the four sections of the unit) and in the isocratic mode (where the pressure is kept constant). However, an almost 3-fold increase in productivity could be achieved in the pressure-gradient rather than the isocratic mode. The obtained results are explained and rationalized using recently developed design criteria for SMBs, the so-called "triangle theory", which have been properly extended to allow for different pressure values in the different sections of the unit.