PECs composed of CH, AV and ALG have been successfully prepared and characterized for potential application in wound healing. The PECs with entrapped active components of AV offer advantages in the wound healing process such as stability, morphology, water absorption, pore size and rigidity. CQCH-6, CBCH-6 and CQCH-6-Ca and CBCH-6-Ca samples produce a high percentage of HDFs viablity. Remarkably, the AV blended with PECs had a positive effect on cell viability and migration. The PECs prepared at pH 4 presented best physicochemical properties notwithstanding significant reductions on HDFs and HLs viabilities. Importantly, none of these PECs displayed cytotoxicity to HLs confirming their biocompatibility and only CQCH-6-Ca presented some diminution on cell viability.Chitosan, sodium alginate and gel of Aloe vera (Aloe barbadensis Miller) were employed for the preparation of polyelectrolyte complexes at pH 4 and 6. FT-IR spectroscopy analysis showed evidence on complexes formation and incorporation of the Aloe vera gel. The ζ potential determination of the polyelectrolyte complexes revealed the presence of surface charges in the range of −20 to −24 mV, which results in stable systems. The dynamic moduli exhibited a high dependence on angular frequency, which is commonly found in solutions of macromolecules. The materials showed human fibroblast and lymphocyte viabilities up to 90% in agreement with null cytotoxicity. The polyelectrolyte complexes at pH 6 with Ca2+ were stable, showed high water absorption, satisfactory morphology, pore size and rigidity, characteristics that allowed significant human fibroblast migration in wound closure in vitro assays.