This research aims at identifying suitable resin adsorbents for efficient separation and purification of alkaloids from plant materials. The adsorption properties (equilibrium, kinetics, and column breakthrough) of four alkaloid model compounds (berberine hydrochloride, ligustrazine hydrochloride, colchicine, and matrine) on selected macroporous resins were studied. The adsorption equilibrium capacities and desorption ratios of the four model compounds on nine different macroporous resins were measured and compared. It was observed that the resins with a low polarity and high surface area offered a high adsorption capacity for all alkaloids. The pseudo-second-order adsorption rate equation fit well all the kinetic data, and the Langmuir and Freundlich isotherm equations correlate well the adsorption isotherms on the four resins. Among the nine resins studied in this work, the HPD300 resin was identified as the most promising adsorbent for alkaloids separation and purification because of its excellent adsorption and desorption properties for all four alkaloid compounds. The adsorption breakthrough experiment on the HPD300 resin using a mixture solution containing all four model compounds further confirmed the effective separation of alkaloids on the HPD300 resin.