Double-layered ternary-phase microparticles composed of a poly(D,L-lactide-co-glycolide) (50:50) (PLGA) core and a poly(L-lactide) (PLLA) shell impregnated with poly(caprolactone) (PCL) particulates were loaded with ibuprofen (IBU) and metoclopramide HCl (MCA) through a one-step fabrication process. MCA and IBU were localized in the PLGA core and in the shell, respectively. The aim of this study was to study the drug release profiles of these double-layered ternary-phase microparticles in comparison to binary-phase PLLA(shell)/PLGA(core) microparticles and neat microparticles. The particle morphologies, configurations and drug distributions were determined using scanning electron microscopy (SEM) and Raman mapping. The presence of PCL in the PLLA shell gave rise to an intermediate release rate of MCA between that of neat and binary-phase microparticles. The ternary-phase microparticles were also shown to have better controlled release of IBU than binary-phase microparticles. The drug release rates for MCA and IBU could be altered by changing the polymer mass ratios. Ternary-phase microparticles, therefore, provide more degrees of freedom in preparing microparticles with a variety of release profiles and kinetics.