The permeability of anti-arrhythmic crude alkaloids (Vingerbine preparation) from Vinca herbaceae W. et Kit. across rat intestine has been demonstrated for the first time. The results suggest that P-glycoproteins (P-gps) are involved in the preferential transport of vincarine and herbadine, compounds bearing a hydrogen atom on a secondary N (N–H), in the basolateral to apical direction. However, P-gp/MDR1 play a minor role in the intestinal transport of herbamine and vincamajine, compounds with substituted N (N–CH3). In order to improve peroral bioavailability and achieve maximum therapeutic efficiency of Vingerbine, further research will be focused on finding a strategy to overcome the P-gp barrier and developing suitable delivery systems.