Evolving knowledge of the structure and physical properties of metallurgical slags is summarized in current review. Slag structure, compositional effects, role of cations in structural modifications, parameters used to represent the structure, structural analysis techniques and effects of structure on properties of blast furnace slag (BFS) studied in details. The basicity, polymerization (Q) or depolymerization (NBO/T), optical basicity, Qn values, concentrations of bridging O’s (Oo), non-bridging O’s (O−) and free O’s (O2−) in slag are useful to represent the structure of slag. Methods and techniques utilized to study the slags are also discussed. The BFS is characterized by using X-ray Diffraction and Spectroscopy, Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Photoelectron Spectroscopy (XPS) and Nuclear Magnetic Resonance (NMR) Spectroscopy. The physical properties such as surface tension, viscosity, density, thermal expansion and diffusion, electrical conductivity and resistivity of slags are reviewed thoroughly which are heavily dependent on structure of slag. Viscosity is affected by polymerization or depolymerization of slag structure and cation size; electrical resistivity depends on Q, size of cations and number of available cations; thermal expansion depends on Q and cation field strength (i.e. z/r2); thermal conductivity is linked with rigidity of slag network which is also dependent on Q and metal-oxygen (M–O) bond strength. Degree of polymerization or depolymerization of slag structure also effect the surface and interfacial tension, it decreases as metal-oxygen (M–O) bond strengths (i.e. z/r2, cation field strength) decrease.