In this study, tetraphenylthiophenen (TP) with aggregation-induced emission enhancement (AIEE) property is served as terminal and central fluorophores of poly(£^-benzyl-L-glutamate) (PBLG)-based polymers of TP1PBLG and TP2PBLG, respectively, to probe for the relationship between the secondary structure (£\-helix) of polypeptides and the ALEE-operative fluorescence (FL). Intermolecular aggregation of the central TP unit in the di-substituted TP2PBLG is sterically blocked by the large £\-helical PBLG chains, which lead to the reduced AIEE-oriented FL. On the contrast, the terminal TP units in TP1PBLG can easily approach each other to form aggregates with strong FL. Factor (e.g. solvent annealing) controlling the fraction of £\-helix chain also varies the corresponding emission intensity. Conformational difference between TP1PBLG and TP2PBLG evaluated from the infrared and the X-ray (wide- and small-angle) diffraction spectra is also used to verify its influence on the AIEE-operative FL behavior.