“The column is the heart of the separation.” Perhaps more accurately, the column is where the chemistry that generates a separation happens. For chemists and non-chemists alike, the chemistry that drives the utility of a column to solve a separation problem can be complex and confusing. Selectivity describes the ability of a column to effect a separation. This instalment of “GC Connections” focuses on selectivity, its definition, and its importance for generating separations and resolution. We will also see how selectivity is the concept that underlies the idea of column polarity. We begin by asking two simple questions about common observations, then extend these observations into a capillary gas chromatography (GC) column, and conclude with an introduction to methods for evaluating the quality, selectivity, and polarity of a stationary phase or column.