Selective laser sintering (SLS) is a powder bed fusion technology that uses a laser source to melt selected regions of a polymer powder bed based on 3D model data. Components with complex geometry are then obtained using a layer-by-layer strategy. This additive manufacturing technology is a very complex process in which various multiphysical phenomena and different mechanisms occur and greatly influence both the quality and performance of printed parts. This review describes the physical phenomena involved in the SLS process such as powder spreading, the interaction between laser beam and powder bed, polymer melting, coalescence of fused powder and its densification, and polymer crystallization. Moreover, the main characterization approaches that can be useful to investigate the starting material properties are reported and discussed.