The release of drugs, entrapped into the poly(allylammonium acrylate) (PAAC) polyelectrolyte complex structure, was tested for vitamin B-12 (VitB12) and tetracycline (TCY). The PAAC-drug "composites" were obtained by synthesizing PAAC in the presence of either VitB12 or TCY. Weighed samples of the "composites" were sintered as tablets, which were dipped into Dulbecco＇s PBS (pH 7.3); the release was followed spectrophotometrically. The tests show very low limiting release values, with different kinetic behaviours for TCY and VitB12. The results are discussed and attributed to strong ionic interactions between the polyelectrolyte complex and the dipolar ions VitB12 and TCY.