Porous organic polymers (POPs) with high surface areas (especially more than 5,000 m2 g−1) are still quite rare. In this work, we implemented the molecular-building-block strategy to isolate three POPs, namely KPOP-1, KPOP-2, and KPOP-3 (KPOP = KAUST's POP), and hypothetically predicted the structures of the three KPOPs. KPOP-1 and KPOP-2 exhibit high specific BET surface areas (ca. 5,120 and 5,730 m2 g−1) and display outstanding gravimetric methane storage properties. Remarkably, the methane uptake of KPOP-2 at 298 K and 80 bar is 0.515 g g−1, surpassing the gravimetric 2012 Department of Energy target for onboard CH4 storage, and KPOP-2 shows the exclusive potential for stationary CH4 storage. Interestingly, KPOP-1 and KPOP-2 show extremely hydrophobic behavior combined with high organic vapor uptakes, a desirable feature enabling effective capturing of volatile organic compounds at room temperature.