Long ago bars were various shapes, starting with square and occasionally hexagonal.
In bending, rebars with corners create significant stress concentrations on the concrete, thus failing the bond. This condition does not occur with round bars under normal loading. Additionally, if other than round, there would be some preferential orientation of the rebar, which makes for difficult construction.
Also, when bending the rebar, square or other corners tend to fracture. Another reason that round cross-sections are used.
Ron