A series of phenylene-containing α,ω-hydroxy-terminated fluorosilicone polymers were synthesized by dehydration polycondensation in the presence of non-equilibrium catalyst from α,ω-hydroxy-terminated poly(methyltrifluoropropyl) siloxanes and phenylene-containing disilanol monomers. The effects of reaction time, catalyst dosage, reactant concentration, and monomer ratio on the appearance, intrinsic viscosity, molecular weight and distribution, and copolymer composition of the obtained polymers were studied. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), rheometer and thermal analysis were utilized to study their chemical structure, room temperature crosslinking reactivity, mechanical property, thermal resistance, and glass transition. The results show that the introduction of phenylene into the main chain not only significantly improves the high temperature resistance of the polymer, but also contributes to the improvement of the crosslinking reaction rate and mechanical properties, and when the phenylene content is lower than 30%(mol), it does not adversely affect the glass transition temperature (Tg) of the polymer. It is reasonable that the insertion of phenylene inhibits the cyclization degradation and simultaneously improves the stiffness of the siloxane chain, which is beneficial to thermal resistance. Besides, the terminal silanol is separated from bulky trifluoropropyl side groups by the insertion of phenylene, and thus their shielding effect is reduced, which is helpful to the crosslinking reactivity. Therefore, the polymers can be utilized to prepare fluorosilicone sealants which show good crosslinking property, physical property, and high and low temperature resistance.