Cellulose acetate aerogel (CAA) regenerated with toluene solvent was first obtained and analysed in this work using several measurement techniques. CAA, a “green” and environmentally friendly material, with high thermal stability, water absorbency and a porous structure is a hopeful candidate as a superabsorbent and potential heat insulator for various applications. The obtained porous aerogel with a notable surface area (312.5 m2/g) is thermally stable up to about 300 °C and super-absorbent (72.0 g water/1.0 g sample). Thereby, the present study can play an important role in developing production of cellulose acetate based “green” absorbent and potential aerogel materials for heat insulating. Moreover, this process is handily available at low cost, sustainable and favourable for many applications.