In this manuscript, neat electrospun poly(o-methoxyaniline) (POMA) fibers were applied for the first time in the growth of neural stem cells. POMA was synthesized by chemical oxidative polymerization, followed by dissolving in tetrahydrofuran/dimethylformamide to prepare electrospinning solution. Subsequently, the solution was electrospun to produce polymeric fibers. The structure, transparency and morphology of as-prepared POMA fibers were characterized by Fourier transform infrared spectroscopy, UV-visible spectroscopy and scanning electron microscopy, respectively. It was found to have no adverse effects on the long-term proliferation of the neural stem cells (NSCs), retain the ability to self-renew, and exhibit multipotentiality. Studies on cell-fiber interactions were carried out by culturing NSCs on the POMA substrate and assessing their growth, cell viability, and differentiation. Results of cell viability assay, immunofluorescence staining, quantitative real-time reverse transcription-PCR and calcium image studies confirmed that POMA electrospun fibers not only showed better NSCs attachment, but also enhanced and accelerated differentiation.