Linear poly(l‐lactides) (PLLAs) and poly(d‐lactides) (PDLAs) with Mn in the range 2000 − 4300 containing a different number and placement of carboxyl groups were obtained via cationic ring‐opening polymerization and post‐polymerization functionalization. PLA stereoisomers (PLLA‐(COOH)x and PDLA‐(COOH)x, where x = 1 − 3) were used for the investigation of stereocomplexation in solution performed in the presence of metal cations such as Ca2+, Mg2+, Zn2+, Fe3+. Spherical microparticles with a diameter in the range 0.7 − 3.0 µm were obtained in all cases which was confirmed on the basis of scanning electron microscopy (SEM) analysis. The microsphere size and homogeneity were analyzed depending on the stereocomplexation conditions and the molecular weight as well as the number of carboxyl end groups in the PLLA and PDLA used for stereocomplexation. The PLA microspheres obtained were analyzed by Fourier transform IR spectroscopy, wide angle X‐ray spectroscopy and energy‐dispersive X‐ray spectroscopy methods which confirmed the presence of metal cations inside. The application of regular microspheres with metal ions as drug delivery systems is considered. © 2016 Society of Chemical Industry