The effect of lignin is a key issue in various cellulose processes. To study the effects of lignin state and content on cellulose electrospinning and fiber properties, two different types of cellulose solutions were prepared and electrospun under several different conditions. One was mixture of cellulose and lignin and the other one was hemp cellulose in which cellulose is naturally combined with lignin. In both the cases, the solutions were stably electrospun when the lignin concentration was lower than 5%. The lignin in the cellulose/lignin mixture resulted in film-like fiber and bimodal distribution of the fiber diameter, while the lignin in the hemp cellulose mainly increased the fiber diameter. It is originated from the different phase separation behaviors of the two solutions. The results can give the fundamental understandings for the roles and action of lignin in cellulose process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40031.