Poly(lactic acid) (PLA) fibers has been obtained by solution blow spinning (SBS) using different solvents, however most of them are toxic and can be dangerous to human health or cause harm to the environment. Therefore, this work aimed to evaluate the use of dimethyl carbonate (DMC), a greener solvent, on the production of PLA fibers by SBS using surface response analysis to evaluate and compare the influence of three solvents (chloroform, DMC, and 1,1,1,3,3,3‐hexafluoro‐2‐propanol, HFP) in the average fiber diameter. Scanning electron microscopy (SEM) was used to analyze the fiber morphology and different ranges of fiber diameter was observed when varying the solvents (chloroform: 260–970 nm; DMC: 240–650 nm; and HFP: 220–470 nm). Regression analysis showed the polymer concentration was significant for all solvents and the air pressure was significant when using chloroform and HFP. Regardless of the air pressure, increasing the PLA concentration increased the average fiber diameters for all solvents. Chloroform and HFP indicated a tendency of reduction on the average fiber diameter when the air pressure was decreased, however this behavior was not observed for DMC. It was also observed that the standard deviation indicated to be more affected by the polymer concentration than by the air pressure. The results also indicated that lower surface tension and viscosity can reduce fiber thickness. All solvents showed to be feasible to produce PLA fibers by SBS and DMC can be used to produce PLA fibers with an affordable price using a greener process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43379.