The doped polyaniline (PANI) with rare earth ions, which exhibits an increasing conductivity and strongly enhanced fluorescence emission, was prepared by dispersing PANI powder suspension in acetonitrile solution containing rare earth ions according to different mass ratios of rare earth ions to PANI at room temperature. The structure of the doped PANI was characterized by the spectra of FTIR, Raman, UV-vis, and XRD. Red-shifted change for the quinoid and benzenoid stretching vibration is observed in IR and Raman spectra after doping rare earth cations, and UV-vis absorption peak also presents a red-shift, indicating that the doped PANI possesses a better delocalization of electrons along the mainchain backbone. The experimental data show that the electrical and optical behaviors of PANI strongly depend on the species of rare earth cations and their concentration. It is found that enhancing fluorescence for the doped PANI is observed by comparing with emeraldine base (EB). Moreover, the conductivity of the protonated PANI samples doped with Eu3+, Tb3+, and Y3+ ions, increases from 2.1 x 10(-4) to 3.33 S cm-1, 1.50 x 10(-1) S cm-1 and 2.26 x 10(-1) S cm-1. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012