The phase separation behaviour and phase morphology of blends of 4,4'-diaminodiphenyl sulphone cured diglycidyl ether of bisphenol-A with poly(e-caprolactone) were investigated by means of scanning electron microscopy, small angle light scattering and optical microscopy. The components are miscible prior to curing. High-temperature isothermal curing induces phase separation. Blends with near to critical concentrations demix via spinodal decomposition. The associated co-continuous morphology is only preserved in the actual critical compositions whereas for off-critical compositions it rapidly breaks up into spherical particles. The proceeding reaction in the separated phases induces a secondary phase separation. Occasionally, tertiary phase separation is observed as well. Off-critical compositions that are further away on either side from the critical point, phase separate via the direct formation of spherical particles, most likely as a result of the dynamic asymmetry of these blends. The influence of the amount, the molar mass of PCL and the cure temperature is discussed. (c) 2005 Elsevier Ltd. All rights reserved.