Four-coordinate organoboron derivatives present interesting chemical, physical, biological, electronical, and optical properties. Given the increasing demand for the synthesis of smart functional materials based on chiral organoboron compounds, the exploration of stereoselective synthesis of boron-stereogenic organo-derivatives is highly desirable. However, the stereoselective construction of organoboron compounds stereogenic at boron has been far less studied than other elements of the main group due to configurational stability concerns. Nowadays, these species are no longer elusive and configurationally stable compounds have been highlighted. The idea is to show the potential of the stereoselective building of the four-coordinate boron centre and encourage future endeavors and developments in the field.