The coupling of molecular excitations to localized surface plasmon resonances (LSPR) in silver or gold nanostructures is at the center of single-molecule detection (SMD) using surface-enhanced Raman scattering (SERS). The effect is attributed to the enhanced scattering power caused by coupling with the surface plasmons of the metal. The most efficient coupling is attained when the excitation is in resonance with the molecule and the nanostructure, the case of surface-enhanced resonance Raman scattering (SERRS). This incredible effect has the potential to be a powerful optical tool when used in conjunction with vibrationally differentiable chromophores. Here we present a unique study where the targeted system is a phospholipid that is tagged with a xanthene dye (the SERRS probe), a chromophore that dominates the Raman signal when the laser is in resonance with its absorption. The labeled phospholipid was incorporated into a single fatty acid Langmuir monolayer at varying concentrations and transferred onto a silver nanoparticle film to form Langmuir-Blodgett (LB) monolayers. Because the xanthene dye is tagged to a much larger molecule, the chances of dye aggregation (formation of dimers or higher aggregates) is negligible. Single-molecule detection of the dye tag (SERRS probe monomer) is readily achieved and demonstrated through the use of doped LB monolayers, Raman microscopy, spectral mapping, and efficient coupling of the laser line into the dye absorption band and plasmon resonances.