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

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.