This paper investigates the critical condition whereby the compressed edge of a beam subjected to large bending exhibits a sudden lateral heeling. This instability phenomenon occurs through a mechanism different from that usually studied in linear theory and known as flexural–torsional buckling. An experimental test device was specifically designed and built to perform pure bending tests on soft materials. Thus, the experimental campaign provides not only the moment-curvature behavior of beams of narrow rectangular cross section, but also information regarding the post-critical lateral buckling behavior. To study the local bifurcation phenomenon, an analytical model is proposed in which a field of small transversal displacements, typical of the linear stability of thin plates, is superimposed on the large vertical displacement field of an inflexed beam in the nonlinear elasticity theory. Furthermore, numerous numerical simulations through nonlinear FE analysis have been performed. Finally, the results provided by the different methods applied were compared and discussed.