Linear low density polyethylene (LLDPE) exhibits a complex molecular structure that is characterized by molar mass and chemical composition distributions. Both molecular parameters complementarily influence the final application properties. Typically, the molecular structure of commercial polyolefins is characterized by a set of technical parameters including the melt flow index, the crystallization and melting temperatures and the comonomer content as obtained using Fourier transform infrared or NMR spectroscopy. LLDPEs with high comonomer contents are typically regarded as plastomers or elastomers. Due to their low crystallinities, characterization of these materials using crystallization‐based analytical techniques is of limited use since the majority of the material is rather amorphous. Such materials need specific alternative analytical methods that may be based on molar mass and/or chemical composition fractionation. Here it is shown that for a comprehensive analysis of LLDPEs with similar bulk properties, preparative molar mass fractionation (pMMF) and advanced analysis of the fractions are required. The pMMF fractions are comprehensively analyzed using size exclusion chromatography, differential scanning calorimetry and high‐temperature high‐performance liquid chromatography to provide detailed information on molar mass and copolymer composition. Correlated information of these molecular parameters is obtained by comprehensive two‐dimensional liquid chromatography. © 2019 Society of Chemical Industry