Methods for characterization of additives in decorative type paint are needed to better understand the underlying chemistry. Little information is given by suppliers, and the complexity of paint makes understanding the chemistry of the components used important to formulate better paints. An in-house made binder emulsion consisting of an anionic and a nonionic surfactant and two in-house made alkyds have been investigated. The emulsion was first destabilized to allow for analysis of the oil phase. The emulsion and surfactant additives were investigated using gel permeation chromatography (GPC) and high-performance liquid chromatoraphy (HPLC), with the intent of creating methods for further characterizing other additives. The structure of the anionic surfactant was elucidated using liquid chromatography mass spectrometry (LC-MS), gas chromatography mass spectrometry (GC-MS) and Fourier-transform infrared spectroscopy (FTIR), and quantified using LC-MS. During the work on destabilizing the alkyd emulsion the heat stability of both anionic and nonionic surfactant was investigated. An offline two-dimensional liquid chromatography (2DLC) method where fractions from GPC were injected onto a reversed-phase liquid chromatography (RPLC) column has been investigated. The structure of an additive used in paint has been determined, and further knowledge regarding off-line 2DLC for paint characterization has been gained, allowing for future additives to be investigated.