In this study, X-ray photoelectron spectroscopy (XPS) was used to study chitosan-graphene oxide (chitosan-GO) incorporated with 4-(2-pyridylazo)resorcinol (PAR) and cadmium sulfide quantum dot (CdS QD) composite thin films for the potential optical sensing of cobalt ions (Co2+). From the XPS results, it was confirmed that carbon, oxygen, and nitrogen elements existed on the PAR-chitosan-GO thin film, while for CdS QD-chitosan-GO, the existence of carbon, oxygen, cadmium, nitrogen, and sulfur were confirmed. Further deconvolution of each element using the Gaussian-Lorentzian curve fitting program revealed the sub-peak component of each element and hence the corresponding functional group was identified. Next, investigation using surface plasmon resonance (SPR) optical sensor proved that both chitosan-GO-based thin films were able to detect Co2+ as low as 0.01 ppm for both composite thin films, while the PAR had the higher binding affinity. The interaction of the Co2+ with the thin films was characterized again using XPS to confirm the functional group involved during the reaction. The XPS results proved that primary amino in the PAR-chitosan-GO thin film contributed more important role for the reaction with Co2+, as in agreement with the SPR results.