The fast growing cosmetic market and the need for innovative products with new or combined properties lead to the development of a large variety of new complex polymer materials. The variations which can be achieved by modifying the monomer composition or the method of synthesis are very useful to produce (co)polymers with peculiar properties. The demand in characterization is then very important to understand the molecular structure of these new products in order to relate them with the observed properties aiming at the establishment of structure-property relationships. Such knowledge allows for optimization of the parameters of the synthesis and consequently the final application properties. The aim of this work was to develop analytical methods and tools to comprehensively characterise the heterogeneities of acrylate- and methacrylate-based copolymers. The focus of the method development was on multidimensional chromatographic techniques that allow the different parameters of molecular heterogeneity (e.g. molar mass distribution, MMD, chemical composition distribution, CCD) to be described quantitatively.