Temperature-responsive PVCL homopolymers and functional PVCL polymers containing carboxylic acids are prepared in organic and aqueous solutions. PVCL bulk polymers are characterized using 1H NMR, photometry, ATR-FTIR, and thermal analysis. A finite phase transition at 3740 degrees C occurs in aqueous solutions of PVCL and PVCL-COOH. PVCL and PVCL-COOH polymers are electrospun into fibers ranging from 100 to 2300nm in diameter. PVCL/cellulose bi-component films are obtained by electrospinning of CA and PVCL followed by alkaline hydrolysis. These tunable thermo-responsive PVCL/cellulose nanofibers have potential applications in developing affinity membranes.