While electrospinning has been widely employed to spin nanofibers, its low production rate has limited its potential for industrial applications. Comparing with electrospinning, centrifugal spinning technology is a prospective method to fabricate nanofibers with high productivity. In the current study, key parameters of the centrifugal spinning system, including concentration, rotational speed, nozzle diameter and nozzle length, were studied to control fiber diameter. An empirical model was established to determine the final diameters of nanofibers via controlling various parameters of the centrifugal spinning process. The empirical model was validated via fabrication of carboxylated chitosan (CCS) and polyethylene oxide (PEO) composite nanofibers. DSC and TGA illustrated that the thermal properties of CCS/PEO nanofibers were stable, while FTIR-ATR indicated that the chemical structures of CCS and PEO were unchanged during composite fabrication. The empirical model could provide an insight into the fabrication of nanofibers with desired uniform diameters as potential biomedical materials. This study demonstrated that centrifugal spinning could be an alternative method for the fabrication of uniform nanofibers with high yield.