Reticular chemistry allows the design and synthesis of mesoporous networks by extending the size of the building blocks. However, interpenetration of the nets easily happens against the designed mesoporous networks, thereby falling short of achieving the intended specific surface area and pore size. Controlling the framework interpenetration has always been a challenge in the synthesis section of reticular chemistry. In this work, based on our previously reported type of highly porous aromatic frameworks (named PAF-1), we extended the tetrahedral building blocks to target an iso-reticular mesoporous PAF-333. A series of Ni(0) ligands with different sizes were employed to confirm that suitable-sized catalyst ligands could successfully inhibit skeleton interpenetration in the coupling reaction through the steric hindrance effect. The obtained mesoporous PAF-333 possessed a pore size of approximately 3.2 nm matching well with the value from the predicted non-interpenetrated structure. PAF-333 showed great high-pressure hydrogen and methane storage potential with a 13.4 wt % H