Historical development of size exclusion chromatography is briefly outlined. The method is introduced as the only widely applicable analytical technique for the determination of molar mass distribution of synthetic and natural polymers. Different procedures of the molar mass determination including column calibration, universal calibration, and light scattering detection are provided. Various separation mechanisms, resolution, efficiency, selectivity, and secondary mechanisms are described. The effect of key operational parameters on the correctness of molar mass is discussed. In addition to the molar mass, the focus is on the characterization of long‐chain branching. Various applications of online viscometer are reviewed.