Poly(styrene-co-(p-vinylbenzyl 4-(3-pyrrolyl)-4-oxobutyrate)) (PSt-VBPOB) containing 16.7 mol% of p-vinylbenzyl 4-(3-pyrrolyl)-4-oxobutyrate (VBPOB) was synthesized by emulsion polymerization, Pyrrole was coupled onto pyrrole moiety of PSt-VBPOB via oxidative polymerization using FeCl3 as a catalyst. Two kinds of conducting polymers, PSt-VBPOB-ox-Py (S) and PSt-VBPOB-ox-Py (E), were prepared. PSt-VBPOB-ox-Py (S) was prepared in THF solution. On the other hand, PSt-VBPOB-ox-Py (E) was obtained in the emulsion. The conductivity of PSt-VBPOB-ox-Py (E) (1.590 S/cm) was much higher than that of PSt-VBPOB-ox-Py (S) (0.022 S/cm). The mechanisms of electrical conductivity enhancement in PSt-VBPOB-ox-Py (E) is proposed. In the PSt-VBPOB-ox-Py (S) particles, polypyrrole was uniformly distributed throughout the particles. On the other hand, polypyrrole links are mainly located on the surface of the PSt-VBPOB-ox-Py (E) particles, giving surface conducting particles.