The carbon-carbon triple bonds have rich π-electrons, which can be used to polymerize to yield the linear conjugated polymer systems. Here, we prepared poly(3-ethynylpyridine) by the polymerization of 3-ethynylpyridine by various transition metal catalysts in a moderate yield. The electro-optical properties of poly(3-ethynylpyridine) were measured and discussed. The cyclic voltamograms of poly(3-ethynylpyridine) exhibited reversible electrochemical behaviors between the doped and undoped peaks.