Poly(phenylene ethynylene)s(P1) with 4-vinylaniline pendant groups were successfully prepared by the Sonogashira coupling polymerization between l,4-diethynyl-2,5-bis(pentyloxy)benzene and 4-[2-(2,5-dibromophenyl)vinyl]-aniline. In comparison with its analogue P2 without amino group,the emission of P1 is only enhanced by aggregation when adding n-hexane into its THF solution,exhibiting an aggregation-induced emission enhancement(AIEE) effect.When methanol or water instead of hexane was added into THF solution,P1,however,didn’t show AIEE.The results indicated that amino groups strengthen the inter-chain and intra-chain interactions in P1 and restrict the non-radiative energy transition. This strategy can provide a platform for developing highly sensitive and efficient bio- and chemosensors. Poly (phenylene ethynylene) s (P1) with 4-vinylaniline pendant groups were successfully prepared by the Sonogashira coupling polymerization between 1,4-diethynyl-2,5-bis dibromophenyl) vinyl] -aniline. In an analogue P2 without amino group, the emission of P1 is only enhanced by aggregation when adding n-hexane into its THF solution, exhibiting an aggregation-induced emission enhancement (AIEE) effect. When methanol or water instead of hexane was added to THF solution, P1, however, did not show AIEE. The results indicated that amino groups strengthen the inter-chain and intra-chain interactions in P1 and restrict the non-radiative energy transition. This strategy can provide a platform for developing highly sensitive and efficient bio- and chemosensors.