The present research discusses the thermal and structural properties of calcium alginate films synthesized by cross linking precursor sodium alginate films with Ca2+ ions. Raman and FTIR spectroscopy analyses evinced the interchange of Na ions with Ca ions. Both techniques revealed a shift of the COO- vibration modes; the symmetrical COO- peak of calcium alginate exhibited a shift towards higher wavenumber (∼14 cm−1) from 1415 cm−1 to 1429 cm−1 in the Raman spectra. TGA and TMA analyses performed under a nitrogen atmosphere revealed that increasing the Ca-molarity and immersion time resulted in an increase in the glass transition temperature (Tg) and the strain deformation of the Ca-alginate film. The increase in Tg can be attributed to the Ca-cross-linking that could restrict the molecular response to temperature change whereas the increased strain could be due to the enhanced entrapment of water between the molecular chains of the polymer.