Laser ionization time-of-flight mass spectrometry was applied to the online monitoring of a styrene monomer and dimer in an emulsion. During the measurement of a styrene monomer oil-in-water emulsion for this study, a styrene dimer, 1,3-diphenylpropane, was dropped into the emulsion. As a result, signal spikes from both analytes occurred simultaneously, which suggested that either the dimer had moved to the monomer droplets or that the monomer and dimer droplets had aggregated. We concluded that this method could be useful for the direct monitoring of monomers and oligomers in the early stages of emulsion polymerization.