With the aim of increasing flexibility in controlling release from microcapsules, mixtures of wall polymers varying in porosity were investigated by phase separation. Eudragit RL and RS (polymethylmethacrylate linear backbone polymers) mixtures differing in polar substituent content and porosity were used as the wall material and were deposited using a non-solvent addition method. Release rates increased with polar group content of the mixtures, using theophylline, potassium dichromate or sodium chloride as model core materials. Theophylline release rate had the same relationship to polar group content as found earlier for urea permeation of cast mixed-polymer films. Release was generally accelerated in these systems when the external medium contained sodium lauryl sulphate as a wetting agent but not consistently, decreasing unexpectedly for RL-theophylline microcapsules. Localized dissolution of core substance was visible microscopically during release from single microcapsules. The release rate was sensitive to agitation intensity only at low wall to core ratios. Temperature change revealed only a single release mechanism for sodium chloride by Arrhenius equation treatment. Puffer ions penetrated coatings readily, changing theophylline release rates and providing clear evidence of diffusion via a pore-capillary mechanism.