For the first time, aniline was doped into the precursors used for preparing Li3V2(PO4)(3), leading to a polyanilne (PANI)-doped Li3V2(PO4)(3). In this work, three samples, having the weight content of aniline 5 wt%, 7 wt% and 10wt%, respectively, were fabricated. The as-prepared samples were characterized by XRD, SEM, and FTIR, respectively. Unfortunately, the obtained XRD patterns of pure Li3V2(PO4)(3) is not very similar to the standard XRD patterns of Li3V2(PO4)(3). But the XRD patterns of the PANI-doped Li3V2(PO4)(3) are consistent with standard XRD patterns of Li3V2(PO4)(3) in some degree. SEM images strongly demonstrated that the weight content of aniline affected the morphologies of the obtained samples greatly, and it seemed that the sample with 7 wt% aniline has the smallest particle size among the obtained samples. Interestingly, the charge-discharge curves revealed that the PANI-doped sample of 7wt% aniline exhibited the largest discarge capacity among the three samples. The possible reasons for above phenomenon were well discussed based on the FTIR spectra and EIS measurement. Showing the sample of PANI-doepd Li3V2(PO4)(3) is the main contribution of this work, though unsatisfactory results were acquired.