An optically inactive polyacetylene, poly((4-carboxyphenyl)acetylene) (poly-1), exhibits an induced circular dichroism (ICD) in the UV-visible region upon complexation with chiral amines and amino alcohols in DMSO and in the film, the sign of which reflects the stereochemistry including bulkiness, type (primary, secondary, or tertiary), and absolute configuration of the amines. Therefore, the polyacetylene dan be used as a novel probe for determining the chirality of amines. Most primary amines and amino alcohols of the same configuration gave the same sign for the induced Cotton effect; however, secondary and/or tertiary amines used in the present study tended to show Cotton effect signs opposite to those of the primary amines and amino alcohols of the same configuration. The magnitude of the ICD likely increases with an increase in the bulkiness of the chiral amines. The complexation dynamics during the formation of the helical structure of poly-1 with chiral amines were investigated on the basis of the spin-spin relaxation behavior and H-1 NMR, CD, and optical rotatory dispersion (ORD) titrations. The complex formation of poly-1 with chiral amines such as 1-(1-naphthyl)ethylamine and 2-amino-1-propanol exhibits a positive nonlinear effect between the enantiomeric excess of the chiral amines and amino alcohols and the observed ellipticity of the Cotton effects. The excess enantiomer bound to poly-1 may induce an excess of a single-handed helix (right- or left-handed helix), which may result in a more intense ICD than that expected from the ee of the amine. Moreover, it was found that the coexistence of achiral amines such as 1-aminoethanol also induced an excess of one helical sense of poly-1.