A new series of TPATTh-based CMPs have been synthesized via a readily synthetic scheme of C–H direct arylation polymerization (DAP) that involves thiophene-flanked arenes, tris[4-(2-thienyl)phenyl]amine (TPATTh) and commercially available multi-brominated aryls, (2,2′,7,7′-tetrabromo-9,9′-spirobifluorene (TBrSBF), 1,3,6,8-tetrabromopyrene (TBrPy), 2,5-dibromopyrazine (DBrPy), and 1,6-dibromopyrene(DBrPz)). Preactivation of the C–H bonds in the aromatic monomers is not required. The resulting TPATTh-based CMPs display good thermal stability. The porosities of the TPATTh-based CMPs are lain on the structures of the multi-brominated aryls. The TPATTh-based CMPs present good fluorescence emission performances either in the solid states or dispersed in the solvents, and show different colors under 365 ​nm fluorescence irradiation. The resulting TPATTh-based CMPs were used to fluorescence sense to I₂, PA, DNP, and o-NP with high Stern-Volmer quenching constants (Ksv).