Two microporous organic frameworks based on adamantane (hereafter denoted as MF-Ads) were fabricated through Sonogashira-Hagihara coupling polycondensation of aryl halides and alkynes. Results show that both types of MF-Ad networks had similar porous properties and exhibited excellent CO2 uptake capacity (72.5 cm(3) g(-1)) and CO2/N-2 selectivity (59.1) at 273 K and 1.0 bar. Taking advantage of the superhydrophobic wettability of the resulting MF-Ad networks, wire mesh scaffolds were used to fabricate superhydrophobic films with polydimethylsiloxane (PDMS) acting as a binder. These films displayed excellent instant hydrocarbon/water separation efficiency (up to 99.6%), which was maintained at a constant level after five repeated cycles. This work provides a novel insight into the fabrication of microporous organic frameworks and extends their applicability to carbon capture and absorption of hazardous organic pollutants.