XPS is very useful to differentiate such 2 samples. The spectral nature of Cu (0) and Cu (2+) XPS is remarkably different. If your Cu 2p core-level spectra contain prominent satellite peaks at higher binding energy side then the sample is Chitosan-CuO nanoparticle composite. If there is no satellite peak, then your sample is Chitosan-Cu nanoparticle composite.
ESCA/XPS is surface sensitive to about 5 - 10 atomic layers. This surface will always be fully oxidized in air. That is, your XPS result will always show Cu in the +2 oxidation state. In order to confirm that this is only a surface effect then one will need to argon ion etch the surface layers and see if the bulk is Cu2+ or Cu 'metal' in the zero oxidation state..