Block and random polyhedral oligomeric silsesquioxane (POSS)/fluorinated poly aryl ether sulfone tricopolymers were synthesized using different synthetic strategies to investigate the effect of sequence distribution on their thermal, dielectric, and surface properties. Analyses indicated that all block and random copolymers showed similar growth tendency of water contact angles and Tg values, downward tendency of k values with increased content of POSS. The block copolymer displayed higher Tg values up to 187°C than random copolymers (173°C) under the same POSS molar percentage, which were highly related to their different sequence distribution. The dielectric constants of the tricopolymers were drastically reduced because of the presence of POSS and fluorine, and the dielectric constant could achieve as low as 2.71 (1 MHz). Besides, sequence distribution has no obvious influence on its surface properties and properties. Meanwhile, the yields of degradation residues of the tricopolymers were significantly improved by the ceramic formation from POSS moieties during thermal decomposition.