We present the study of silver nanocube (Ag NC)-enhanced fluorescence of a cationic conjugated polyelectrolyte (CPE) for far-red/near-infrared fluorescence cell imaging. Layer-by-layer self-assembly of polyelectrolytes on 78 nm Ag NCs is used to control CPE-metal distance and its effect on CPE fluorescence. The highest fluorescence enhancement factor (FEF) is obtained for Ag NCs with two bilayers, corresponding to a CPE-metal spacer thickness of ~6 nm. At the optimal excitation wavelength, the FEF is 13.8 with respect to the control silica nanoparticles (NPs). The fluorescent NPs are further used for cellular imaging studies. The CPE-loaded Ag NCs with two bilayers exhibit excellent image contrast, superior to the control of CPE-silica NP at a similar uptake efficiency. The viability test indicates low cytotoxicity of the CPE-loaded Ag NCs, rendering them as promising cell imaging agents.