Our scanning tunneling microscopy and electron diffraction experiments revealed that a new two-dimensional allotrope of Bi forms on the Si(111)-7x7 surface. This pseudocubic [012]-oriented allotrope is stable up to four atomic layers at room temperature. Above this critical thickness, the entire volume of the film starts to transform into a bulk single-crystal (001) phase, as the bulk contribution in the cohesion becomes dominant. Based on ab initio calculations, we propose that the new allotrope consists of black phosphorus-like puckered layers stabilized by saturating all the p(z) dangling bonds in the film.