Molecularly imprinted polymers (MIPs) selective for Tröger’s base were designed and synthesised, and HPLC-chromatographic evaluation of polymer recognition characteristics was undertaken. Baseline separation of racemic Tröger’s base was readily achieved, and enantioseparation factors (α) of up to 4.8±0.2 were obtained. The high enantioselectivity demonstrated by these materials prompted their use to examine the kinetics and thermodynamics of individual enantiomers in a solid-phase extraction (SPE) process. Enantiomer-dependent differences in the rates and extent of adsorption were observed. Furthermore, the enantiomeric enrichment of racemates was demonstrated in batch studies.