The literature on the use and theory of silver(I) complexation (argentation) chromatography is reviewed. Apolar isomeric alkenes, for example numerous terpenes and fatty acids, can be well resolved by means of high pressure liquid chromatography on cation exchange materials coated with silver(I) ions, but unfortunately the mechanism on which these separations are based is not fully understood. As part of an attempt to provide a predictive model for the separation of volatile alkenes, the retention of more than 40 C2‐C10 olefins besides a number of C14‐pheromones and volatile terpenes is given and the results discussed. The separation is mainly governed by the type and number of double bonds (isolated, conjugated or aromatic), their steric accessibility (number and size of substituents) for complexation with silver(I) ions, the relief of inherent strain upon complexation and electron donating or withdrawing groups, or polar groups close to the double bond. Polar groups such as hydroxyls also complex weakly with silver. Other functional groups, including carbonyls, and the overall polarity of the solute play only a minor role. Similarly most solvents have only a limited influence on the selectivity and speed of separation, and function more as a transportation medium as in gas chromatography. A comparative model which gives semi‐quantitative estimations of the retention time of most volatile olefins in methanol is presented. Substituent parameters (Ags) which quantitatively forecast the influence of different alkyl side chains are part of this model.