Silver thin films are well known as the most sensitive material for surface plasmon resonance (SPR) based analysis. However, the use of silver for this purpose is limited by three main issues, namely poor adhesion to plastic substrates, chemical instability in both air and aqueous environments and hence the difficulty in functionalizing the silver coated substrate for immobilizing biomolecular ligands by conventional liquid phase methods. In this work, we have successfully addressed these problems using gas-phase coating processes. We demonstrate highly adherent sputter-deposited silver coatings on low cost polymer substrates using a sputter-deposited thin gold adhesion layer. The problems of chemical instability and functionalisation have been addressed by using the gas phase process of plasma enhanced chemical vapour deposition (PECVD) to deposit thin films with a base SiO(x)C(y)H(z) layer (using tetraethyl orthosilicate precursor) functionalised with carboxylic acid (from sequential deposition with acrylic acid precursor). The resultant coating serves as a protective layer against degradation of the optical properties of silver under long term storage and use in ambient conditions. The reactive carboxyl functionality is used for the covalent immobilization of biomolecules. The successful stabilisation and functionalization of silver films on plastic sensor chips is demonstrated by mouse IgG immunoassays. The expected superior performance of the silver thin films over gold thin films for SPR analysis is demonstrated.