Capillary electrophoresis (CE) has been widely used in the study of the interactions between targets (biological macromolecules) and ligands due to its good biocompatibility. However, the separation and analysis of platelets, which play a pivotal role in thrombotic diseases, were limited owing to platelets adhesion in inner wall of capillary during CE analysis. In this paper, polyvinyl alcohol-coated capillaries were simply prepared to prevent the adhesion of platelet. Then, a frontal analysis CE (FACE) method was developed to evaluate the interactions between platelets and eight alkaloids include glaucine, magnoflorine, dehydrocorydaline, palmatine, berberine, isorhynchophylline, rhynchophylline, and brucine. The binding constants and stoichiometries of the interactions were calculated by Scatchard equation for strong and specific interaction, and the non-specific binding equation for weak interaction. The results indicated that glaucine, dehydrocorydaline, and isorhynchophylline showed relatively high affinity interaction with platelets. The developed FACE method may be further applied in the evaluation of interactions between platelets and other small molecular compounds.