Cylindrical-electrode-assisted solution blowing spinning (CSBS) is a novel method for preparing polymer nanofibers by using air-stretch and electrostatic simultaneously, which can fabricate thinner and more uniform nanofibers than the traditional solution blowing spinning (SBS). In this work, the effects of processing parameters including length of cylinder (LC), needle to cylinder distance (NCD) and left face of cylinder to collector distance (CCD) on the CSBS nanofiber diameter were investigated. The results are as follows: when the NCD decreased, the fiber diameter decreased; when the LC increased, the fiber diameter decreased; the CCD didn’t significantly affect the fiber diameter. Moreover, an orthogonal experimental design was utilized to investigate the effect of injection rate, air pressure, NCD, LC, diameter of cylinder (DC), voltage and CCD on the fiber diameter and porosity of various surface layers of nanofiber web (P1, P2, and P3). The results showed that the varied range of each properties (average diameter, standard deviation of the diameter, P1, P2, and P3) was 539.121-904.149 nm, 127.903-303.253, 71.464-85.1415%, 60.32725-75.46625%, 48.23925-70.08875%, respectively. We also found the order of the influence of the above-mentioned seven process parameters on each above properties of the nanofiber web, and the corresponding optimal spinning process parameters were listed. It is well known that the fiber diameter affects the mechanical properties of nanofibers, and porosity of nano-fiber webs is an important parameter in tissue engineering, bioengineering, and filtration. The effects of CSBS process parameters on nanofiber morphology and microstructure were investigated for the first time. The conclusion of the paper can help researchers to produce high quality CSBS nanofiber and promote the wider application of this novel technology.