In plane aligned nanofibers of organic 2-methyl-4-nitroaniline (MNA) were produced by the electrospinning technique using a 1:1 Weight ratio with poly(L-lactic acid). The fibers are capable of enormous efficient optical second harmonic generation as strong as pure MNA crystals in powder form: Structural, spectroscopic, and second harmonic generation polarimetry studies show that the MNA crystallizes within the fibers in an orientation in which the aromatic rings of MNA are predominantly orientated edge on with respect to the plane of the fiber array and with their dipole moments aligned with the fiber axis. The results show that the electrospinning technique is an effective method to fabricate all-organic molecular functional devices based on polymer nanofibers with guest molecules possessing strong nonlinear optical and/or polar properties.