In this research, nanocomposite nanofibrous webs of poly(acrylic acid) (PAA)/multi‐walled carbon nanotubes (MWNTs) were obtained via electrospinning. The effect of MWNTs concentration on the morphology and mechanical properties of PAA/MWNTs nanofibers was investigated by changing the MWNTs content from 0 to 5 wt%. The results showed that average diameter of nanofibers increased with increasing the MWNTs concentration and presence of MWNTs led to the enhancement of mechanical properties. Also, the results revealed that the strength, modulus, and elongation at break of samples increased 3.22, 2.70, and 4.27 fold, respectively, after adding 3 wt% of MWNTs. In addition, the effect of rotating speed of collector on the orientation of PAA nanofibers and its effect on mechanical properties was investigated. Scanning electron microscopy (SEM) studies demonstrated that the degree of nanofibers orientation increased with the augmentation of drum speed to 25 rps. Moreover, the average nanofibers diameter decreased with the increase of drum speed. Improvement of nanofiber orientation resulted in superior mechanical properties that is, higher strength and modulus of aligned nanofiber layers were obtained in comparison to nonaligned layers (12.6 and 26.6 fold, respectively). POLYM. COMPOS., 37:3149–3159, 2016. © 2015 Society of Plastics Engineers