In this study, we reported the first example of enhanced photoluminescent (PL) emission by complexing bulky camphorsulfonic acid (CSA) to organic and polymeric materials containing quinoline moiety. Small-molecule 2,4-diphenylquinoline (DPQ) and poly(vinyl 2,4-enylquinoline) (PVQ) were prepared primarily and complexed with equivalent amounts of CSA to generate the DPQ-CSA and PVQ-CSA complexes, respectively. All samples show the character of aggregation-induced emission (AIE); however, DPQ-CSA and PVQ-CSA complexes have higher emission intensities than their respective precursors of DPQ and PVQ. The CSA-complexation tends to hamper the molecular rotations and leads to the observed emission enhancement.