Electrospinning is one of the most popular techniques for generating fibres with the diameters ranged from tens of nanometers to several micrometers. The properties of as-spun nanofibres including crystallizability, mechanical performances, and biofunctioning are controlled and affected by several parameters, e.g., electrospinning solvent, temperature, humidity, and polymer characteristics. In order to re-verify the theory that the morphology of electrospun nanofibres is influenced by solvents used to dissolve polymer, the present study was carried out in which polymethyl methacrylate (PMMA) was chosen as the solute and processed into nanofibres by means of electrospinning. Seven solvents were separately used to dissolve PMMA at the concentration of 0.06 g/mL. As a result, ring-like, bead-like, ultrafine, and nano-porous nanofibres were generated from PMMA solutions by electrospinning. Because all solvents used in this study dissolved PMMA readily, the different morphologies were not due to their abilities to dissolve PMMA, but rather due to other properties such as boiling points, molecular weight, and molecular structure. Therefore, ring-like PMMA fibres was obtained due to the high boiling point (110 degrees C) and stereo-hindrance effect of toluene. Bead-like nanofibres were generated from PMMA/chloroform and PMMA/dichloromethane solutions. Moreover, two kinds of ultrafine nanofibres were produced through electrospinning of PMMA/1,1,1,3,3,3-hexafluoro-2-propanol, and PMMA/2,2,2-trifluoroethanol solutions.