Hydrogel materials capable of loading and releasing functional proteins have attracted extensive attention. In this study, phycocyanin-loaded polyacrylamide/calcium alginate/calcium carbonate (PC@PAM/CaAlg/CaCO₃) composite hydrogel films were fabricated by combining a PAM/CaAlg polymer network with in-situ CaCO₃ mineralization. This mineralization strategy provided an additional structural approach for regulating film swelling and PC transport. The effects of the acrylamide/sodium alginate (AM/NaAlg) mass ratio and Na₂CO₃ concentration on swelling and PC release in phosphate-buffered saline (PBS, pH 7.4) were investigated. The AM/NaAlg ratio of 4:1 resulted in relatively high swelling and PC release, whereas the PC diffusion was substantially restricted at 12:1. The film prepared at 8:1 and treated with 0.20 wt.% Na₂CO₃ exhibited relatively high swelling and gradual, sustained PC release. This film showed antibacterial inhibition rates of 67.27% against S. aureus and 52.45% against E. coli, while ABTS and DPPH radical-scavenging efficiencies reached 98.29% and 79.68%, respectively.