Negative Differential Resistance (NDR) was studied in details on the MEH-PPV decorated electrospun TiO2 mat. The TiO2 nanofibrous mat was fabricated by the electrospinning method and the as-fabricated mat was decorated with MEH-PPV through simple chemical bath deposition method. The peak-to-valley ratio of the NDR was 1.85. The observed phenomenon was light dependent, i.e., under light that NDR disappeared completely. We have examined that though in the wavelength region of 650-675 nm the NDR could sustain, for other wavelengths in the visible spectrum, it has been ceased to exist. The NDR behavior was steady and stable over several cycles.