In chemistry, pi stacking (also called π–π stacking) refers to the presumptive attractive, noncovalent pi interactions (orbital overlap) between the pi bonds of aromatic rings.  However this is a misleading description of the phenomena since direct stacking of aromatic rings (the "sandwich interaction") is electrostatically repulsive. What is more commonly observed (see figure to the right) is either a staggered stacking (parallel displaced) or pi-teeing (perpendicular T-shaped) interaction both of which are electrostatic attractive For example, the most commonly observed interactions between aromatic rings of amino acid residues in proteins is a staggered stacked followed by a perpendicular orientation.  Sandwiched orientations are relatively rare.
Pi stacking is repulsive as it places carbon atoms with partial negative charges from one ring on top of other partial negatively charged carbon atoms from the second ring and hydrogen atoms with partial positive charges on top of other hydrogen atoms that likewise carry partial positive charges. In staggered stacking, one of the two aromatic rings is offset sideways so that the carbon atoms with partial negative charge in the first ring are placed above hydrogen atoms with partial positive charge in the second ring so that the electrostatic interactions become attractive. Likewise, pi-teeing interactions in which the two rings are oriented perpendicular to either other is electrostatically attractive as it places partial positively charged hydrogen atoms in close proximity to partially negatively charged carbon atoms.  An alternative explanation for the preference for staggered stacking is due to the balance between van der Waals interactions (attractive dispersion plus Pauli repulsion).
These staggered stacking and π-teeing interactions between aromatic rings are important in nucleobase stacking within DNA and RNA molecules, protein folding, template-directed synthesis, materials science, and molecular recognition.  Despite the wide use of term pi stacking in the scientific literature, there is no theoretical justification for its use.