Zein/poly(L-lactide) (PLLA) nanofibers were prepared by blend, coaxial and double-nozzle electrospinning techniques. The effects of different electrospinning techniques on the morphology, crystallization behavior and mechanical property were investigated by environmental scanning electron microscope (ESEM), transmission electron microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), differential scanning calorimeter (DSC), Thermogravimetric Analyser (TGA) and mechanical tests. The electrospun zein/PLLA nanofibers showed the cross section with different shapes compared with pure zein nanofiber. With increasing PLLA into electrospun zein nanofibers, the crystallization behaviors were influenced by the PLLA component on account of the crystal growth and chain diffusion. The PLLA component existing in isolation in double-nozzle electrospinning barely impeded the performance of PLLA. The impeding effect increased in coaxial electrospinning process due to the zein shell coated the PLLA core. If PLLA and zein were distributed uniformly in blend electrospinning, the crystallinity of PLLA was obviously reduced. The double-nozzle nanofibers showed the best mechanical properties in three different nanofibers, it may be due to the crucial role of PLLA nanofibers existing in isolation. Zein/PLLA electrospun mats, prepared by the three electrospinning techniques, combined the advantages of both synthetic and natural materials for its application. The investigation on the effects of different electrospinning techniques on the properties of nanofibers would provide a theoretical basis for the selection in the nanoscaffolds process.