The screening of molecular targets benefits greatly from rational design criteria, which can detect the most promising candidates. We demonstrate that π-depleted polyaromatic molecules present superior π-stacking ability. This counterintuitive realization is quantified using a novel computational criterion, LOLIPOP that identifies π-conjugated frameworks presenting the desired electronic features. The utility of the LOLIPOP criterion is demonstrated by identifing chemosensors presenting enhanced π-stacking ability.