Poly(ε-caprolactone) [PCL] and poly(vinyl acetate) [PVAC] were blended by melt blending through single screw extruder and solution blending with tetrahydrofuran (THF) as solvent. Scanning electron microscope [SEM] in conjunction with thermogravimetry [TG] confirmed the complete miscibility of the polymers. Results obtained from the mechanical tensile testing of blends indicated a significant increase in the Young's modulus, ultimate strength and percentage elongation at breakage over pure polymers suggesting synergism in the polymer blend. The thermal degradation of the pure and blend polymers were studied in nitrogen environment in TG analyzer. The TG, DTG profiles showed the validity of simple linear additive rule suggesting the absence of interaction between the polymers during the pyrolytic degradation. This indicates that though the mechanical properties of the blend exhibit the synergism, the thermal degradation of the polymer blend shows no interaction. © 2004 Elsevier Ltd. All rights reserved.