The detection and discrimination of chiral analytes has always been a topical theme in food and pharmaceutical industries and environmental monitoring, especially when dealing with chiral drugs and pesticides, whose enantiomeric nature assessment is of crucial importance. The typical approach matches novel chiral receptors designed ad hoc for the discrimination of a target enantiomer with emerging nanotechnologies. The massive synthetic efforts requested and the difficulty of analyzing complex matrices warrant the ever-growing exploitation of sensor array as an alternative route, using a limited number of chiral or both chiral and achiral sensors for the stereoselective identification and dosing of chiral compounds. This review aims to illustrate a little-explored winning strategy in chiral sensing based on sensor arrays. This strategy mimics the functioning of natural olfactory systems that perceive some couples of enantiomeric compounds as distinctive odors (i.e., using an array of a considerable number of broad selective receptors). Thus, fundamental concepts related to the working principle of sensor arrays and the role of data analysis techniques and models have been briefly presented. After the discussion of existing examples in the literature using arrays for discriminating enantiomers and, in some cases, determining the enantiomeric excess, the remaining challenges and future directions are outlined for researchers interested in chiral sensing applications.