The purpose was to interpret the varying morphology of electrospun cellulose acetate (CA) fibres produced from single and binary solvent systems based on solubility parameters to identify processing conditions for the production of defect-free CA fibrous webs by electrospinning. The Hildebrand solubility parameter (<svg style="vertical-align:-0.1638pt;width:8.9125004px;" id="M1" height="12.4375" version="1.1" viewBox="0 0 8.9125004 12.4375" width="8.9125004" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"> <g transform="matrix(.017,-0,0,-.017,.062,12.162)"><path id="x1D6FF" d="M494 514l-10 -15q-56 76 -106.5 117t-110.5 41q-45 0 -45 -30q0 -28 109 -152q59 -68 86 -118.5t27 -107.5q0 -62 -29.5 -119.5t-86.5 -96.5q-64 -45 -138 -45q-76 0 -121.5 53t-45.5 136q0 74 40.5 135t98.5 95q43 26 87 42q-40 59 -57.5 92t-17.5 62q0 46 39 77.5
t90 31.5q54 0 97.5 -35.5t65 -78.5t28.5 -84zM359 234q0 84 -90 191q-47 -17 -74 -47q-81 -89 -81 -200q0 -71 32.5 -109.5t72.5 -38.5q47 0 80 33t46.5 77.5t13.5 93.5z" /></g> </svg>) and the radius of the sphere in the Hansen space (<svg style="vertical-align:-5.73167pt;width:41.137501px;" id="M2" height="18.3125" version="1.1" viewBox="0 0 41.137501 18.3125" width="41.137501" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"> <g transform="matrix(.017,-0,0,-.017,.062,11.113)"><path id="x1D437" d="M780 372q0 -191 -178 -297q-128 -75 -335 -75h-250l7 27q61 7 77 22t28 76l77 398q11 62 0 76.5t-77 22.5l6 28h292q164 0 258.5 -67.5t94.5 -210.5zM678 375q0 119 -73 180.5t-201 61.5q-62 0 -82 -13q-17 -7 -25 -53l-80 -427q-8 -47 -4 -62t26 -20q24 -6 80 -6
q166 0 262.5 95t96.5 244z" /></g> <g transform="matrix(.012,-0,0,-.012,13.712,15.188)"><path id="x28" d="M300 -147l-18 -23q-106 71 -159 185.5t-53 254.5v1q0 139 53 252.5t159 186.5l18 -24q-74 -62 -115.5 -173.5t-41.5 -242.5q0 -130 41.5 -242.5t115.5 -174.5z" /></g><g transform="matrix(.012,-0,0,-.012,17.829,15.188)"><path id="x1D460" d="M352 391q0 -31 -27 -44q-14 -7 -24 6q-39 48 -84 48q-23 0 -39.5 -15t-16.5 -40q0 -43 73 -90q49 -32 70 -58t21 -57q0 -58 -62 -105.5t-129 -47.5q-40 0 -75.5 25t-35.5 52q0 28 32 46q7 4 15 3t11 -6q19 -31 48.5 -50.5t54.5 -19.5q34 0 54 19.5t20 42.5q0 43 -65 81
q-97 56 -97 123q0 50 51 96q19 17 58 32.5t62 15.5q37 0 61 -18t24 -39z" /></g><g transform="matrix(.012,-0,0,-.012,22.291,15.188)"><path id="x2212" d="M535 230h-483v50h483v-50z" /></g><g transform="matrix(.012,-0,0,-.012,29.276,15.188)"><path id="x1D45D" d="M570 304q0 -108 -87 -199q-40 -42 -94.5 -74t-105.5 -43q-41 0 -65 11l-29 -141q-9 -45 -1.5 -58t45.5 -16l26 -2l-5 -29l-241 -10l4 26q51 10 67.5 24t26.5 60l113 520q-54 -20 -89 -41l-7 26q38 28 105 53l11 49q20 25 77 58l8 -7l-17 -77q39 14 102 14q82 0 119 -36
t37 -108zM482 289q0 114 -113 114q-26 0 -66 -7l-70 -327q12 -14 32 -25t39 -11q59 0 118.5 81.5t59.5 174.5z" /></g><g transform="matrix(.012,-0,0,-.012,36.332,15.188)"><path id="x29" d="M275 270q0 -296 -211 -440l-19 23q75 62 116.5 174t41.5 243t-42 243t-116 173l19 24q211 -144 211 -440z" /></g> </svg>) of acetone, acetic acid, water, <i >N,N</i>-dimethylacetamide (DMAc), methanol, and chloroform were examined and discussed for the electrospinning of CA. The Hildebrand solubility parameter (<svg style="vertical-align:-0.1638pt;width:8.9125004px;" id="M3" height="12.4375" version="1.1" viewBox="0 0 8.9125004 12.4375" width="8.9125004" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"> <g transform="matrix(.017,-0,0,-.017,.062,12.162)"><use xlink:href="#x1D6FF"/></g> </svg>) of acetone and DMAc were found to be within an appropriate range for the dissolution of CA. The suitability of the binary solvent system of acetone: DMAc (2 : 1) for the continuous electrospinning of defect-free CA fibres was confirmed. Electrospun webs exhibited improved tensile strength and modulus after heat and alkali treatment (deacetylation) of the as-spun material, and no major fibre morphological degradation occurred during the deacetylation process.