We obtained chitosan-protected Au/Ag nanocages (NCs), i.e., hollow and porous metallic nanoparticles, by galvanic replacement reaction. Subsequently, we functionalized the NCs with a fluorescent derivative of 4-methoxy-1,8-naphtalimide (NAFTA6). The plasmonic properties of these structures, which exhibit an extinction maximum in the 700-800 nm range, allowed their use as SERS active substrates for excitation at 785 nm and an efficient identification of the vibrational bands of NAFTA6, in spite of the low ligand concentration (<10(-5) M). Furthermore, NAFTA6 could also be identified from its fluorescence emission. The proposed functionalization with fluorescent compounds opens the way to the application of metal NCs using double-wavelength detection. Namely, Raman spectroscopy in the near infrared and fluorescence emission in the visible region, with considerable potential especially for in vivo medical applications, as the plasmonic band is centered in the visible light region where biological fluids and tissues are transparent. (C) 2013 Elsevier Inc. All rights reserved.