Two novel hyper-cross-linked fluorinated microporous polyketone networks (FMPN-1 and FMPN-2) with permanent porosity and narrow pore size distribution were synthesized via a facile “one-step” polycondensation between the trifluoroacetophenone-based monomers and 1,3,5-triphenylbenzene. The result polymers were investigated by FTIR, solid state NMR, EDX, XRD, TGA, SEM, and TEM et al. The geometry configurations difference of building blocks resulted in the polyketone networks exhibiting the BET special surface areas from 622 to 706 m2 g−1 and total volume from 0.58 to 0.66 cm3 g−1. What's more, ideal adsorbed solution theory (IAST) analysis showed that the two polymers possessed good C3H8/CH4, C2H6/CH4 selectivities at 298K/1 bar. Together with the excellent thermal and physicochemical stabilities, the microporous fluorinated polyketone networks obtained in this work showed promising applications in adsorption/separation for C1–C3 hydrocarbons.