FTIR and NMR spectroscopy and ab initio calculations were applied to understand the nature of enantioselection in the hydrogenation of the heteroaromatic ring in furan- and benzofurancarboxylic acids over cinchonidine-modified Pd. Most probably, cinchonidine adsorbs on Pd, via its quinoline moiety, approximately parallel to the surface, and the protonated quinuclidine N atom and the OH function of the alkaloid form a cyclic complex with the deprotonated acid dimer (2:1 acid:cinchonidine). The acid dimer adsorbs via the electron-rich furan ring and the carboxylate groups close to parallel to the Pd surface; the furan O atom points toward the OH function of cinchonidine. In this position, hydrogen uptake from the Pd surface results in the (S)-enantiomer as the major product. Another cyclic complex (1:1) involving cinchonidine and only one acid molecule is also feasible in solution, but this rigid structure is thermodynamically less favored, and it may be difficult to fulfill the geometric constraints imposed by adsorption on the metal surface.