An effective surface-enhanced Raman scattering (SERS) template based on a 3D hybrid Ag nanocluster (NC)-decorated ZnO nanowire array was fabricated through a simple process of depositing Ag NCs on ZnO nanowire arrays. The effects of particle size and excitation energy on the Raman scattering in these hybrid systems have been investigated using rhodamine 6G as a standard analyte. The results indicate that the hybrid nanosystem with 150nm Ag NCs produces a larger SERS enhancement factor of 3.2 × 10, which is much higher than that of 10nm Ag NCs (6.0 × 10) under 532nm excitation energy. The hybrid nanowire arrays were further applied to obtain SERS spectra of the two-photon absorption (TPA) chromophore T7. Finite-difference time-domain simulations reveal the presence of an enhanced field associated with inter-wire plasmon coupling of the 150nm Ag NCs on adjacent ZnO nanowires; such a field was absent in the case of the 10nm Ag NC-coated ZnO nanowire. Such hybrid nanosystems could be used as SERS substrates more effectively than assembled Ag NC film due to the enhanced light-scattering local field and the inter-wire plasmon-enhanced electromagnetic field. © 2009 IOP Publishing Ltd.