Relationships Between Defectivity and Porosity in High Surface Area Porous Aromatic Frameworks**

Abstract Porous aromatic framework (PAF) microporosity is known to be strongly dependent on synthetic approach but little is known about why certain reactions yield significantly and consistently more porous PAFs. This article explores the connections between synthetic pathway, PAF defectivity, and microporosity. Using a network disassembly strategy, we show that defectivity is highly dependent on synthetic approach and that more defective PAFs are associated with lower surface areas and pore volumes. This empirical association is corroborated through systematic introduction of defects to a modelPAF, which results in significant reduction of apparent surface area and pore volumes. Taken together, these data suggest that only highly efficient coupling reactions should be targeted for the synthesis of ultra‐high surface area porous aromatic frameworks.