Record Ultralarge‐Pores, Low Density Three‐Dimensional Covalent Organic Framework for Controlled Drug Delivery**

Abstract The unique structural characteristics of three‐dimensional (3D) covalent organic frameworks (COFs) like high surface areas, interconnected pore system and readily accessible active sites render them promising platforms for a wide set of functional applications. Albeit promising, the reticular construction of 3D COFs with large pores is a very demanding task owing to the formation of interpenetrated frameworks. Herein we report the designed synthesis of a 3D non‐interpenetrated stp net COF, namely TUS‐64, with the largest pore size of all 3D COFs (47 Å) and record‐low density (0.106 g cm −3 ) by reticulating a 6‐connected triptycene‐based linker with a 4‐connected porphyrin‐based linker. Characterized with a highly interconnected mesoporous scaffold and good stability, TUS‐64 shows efficient drug loading and controlled release for five different drugs in simulated body fluid environment, demonstrating the competency of TUS‐64 as drug nanocarriers.