Thermal and spectroscopic charaterization of PVA, iota carrageenan (IC), and their interpolymer complexes were studied in terms of stability, complex formation, and species determination by XRF, FTIR, Raman, DSC, and TGA. Thermogravimetry analysis showed that initial thermal degradation temperature of PVA/IC decreased from 276 to 256 degrees C with an increase of IC content. The complexation of IC to PVA significantly increased, the thermal stability of IC, where as the thermal stability of PVA increased rather insignificantly. Fourier Transform Infrared (FTIR) and Raman spectroscopic results showed that PVA interacted with IC through ?OH groups of PVA and IC as shown by the frequency and scattering shift at ?OH band of FTIR and Raman spectra of each complex. The involvements of ester sulfate and ether groups of IC in interaction were not significant. In the results of the thermal and spectroscopic analysis, 17% content of PVA/IC is the most miscible and intercomplexable weight fraction of PVA/IC. The natural source of IC, which was unknown was characterized by XRF and found to be as potassium salt and Euchema specie of marine red algee of the class Rhodophceae. (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012