Ab initio calculations at the MP2(full)/6-31++ G**, RI-MP2(full)/6-31++G**, and RI-MP2(full)/6-311++G(2d, 2p) levels of theory demonstrate important synergic effects between two noncovalent interactions that involve aromatic rings, that is, cation-pi and pi-pi interactions. The presence of a cation interacting with the pi cloud of an aromatic ring favors the face-to-face stacking interaction with additional aromatic rings. This effect is extended in the space up to five stacked aromatic rings.