Temperature‐triggered switchable nanofibrous membranes are successfully fabricated from a mixture of cellulose acetate (CA) and poly(N‐isopropylacrylamide) (PNIPAM) by employing a single‐step direct electrospinning process. These hybrid CA‐PNIPAM membranes demonstrate the ability to switch between two wetting states viz. superhydrophilic to highly hydrophobic states upon increasing the temperature. At room temperature (23 °C) CA‐PNIPAM nanofibrous membranes exhibit superhydrophilicity, while at elevated temperature (40 °C) the membranes demonstrate hydrophobicity with a static water contact angle greater than 130°. Furthermore, the results here demonstrate that the degree of hydrophobicity of the membranes can be controlled by adjusting the ratio of PNIPAM in the CA‐PNIPAM mixture.