A high solids content n-butyl acrylate/methyl methacrylate emulsion copolymerization process carried out under starved semi-batch conditions was for the first time monitored on-line by means of Fourier transform (FT)-Raman spectroscopy. Partial least squares regression was employed to build calibration models that allowed relating the spectra with solids content (overall conversion), free amounts of both n-butyl acrylate (n-BA) and methyl methacrylate (MMA), and cumulative copolymer composition. In spite of the heterogeneous nature of the polymerization, the similarities of the spectra for MMA, n-BA, and for the copolymer, and the low monomer concentrations in the reactor, the FT-Raman spectroscopy has been shown to be a suitable noninvasive sensor to accurately monitor the process. Therefore, it is well suited for on-line control of all-acrylic polymerization systems.