A series of composite fibers composed of multi-walled carbon nanotube (MWCNT) and poly(vinyl alcohol) (PVA) are prepared by varying co-flowing wet-spinning conditions such as spinning geometry and PVA concentration, which affect aligning shear stress for MWCNTs during the wet-spinning. Then, structural features, mechanical and electrical performances of MWCNT/PVA composite fibers are investigated as a function of the aligning shear stress of the wet-spinning process. SEM images of the composite fibers exhibit that MWCNTs are wetted effectively with PVA chains. Polarized Raman spectra confirm that the alignment of MWCNTs is enhanced along the composite fiber axis with increasing the aligning shear stress of the spinning process. Accordingly, initial moduli and tensile strengths of the composite fibers are significantly increased with the increment of the aligning shear stress. In addition, it is found that electrical conductivities of MWCNT/PVA composite fibers increase slightly with the aligning shear stress, which is associated with the formation of efficient electrical conduction paths caused by well-aligned MWCNTs along the composite fiber axis.