In recent experiments [M. Dubois, B. Dem\'e, T. Gulik-Krzywicki, J.-C.
Dedieu, C. Vautrin, S. D\'esert, E. Perez, and T. Zemb, Nature (London) Vol.
411, 672 (2001)] the spontaneous formation of hollow bilayer vesicles with
polyhedral symmetry has been observed. On the basis of the experimental
phenomenology it was suggested [M. Dubois, V. Lizunov, A. Meister, T.
Gulik-Krzywicki, J. M. Verbavatz, E. Perez, J. Zimmerberg, and T. Zemb, Proc.
Natl. Acad. Sci. U.S.A. Vol. 101, 15082 (2004)] that the mechanism for the
formation of bilayer polyhedra is minimization of elastic bending energy.
Motivated by these experiments, we study the elastic bending energy of
polyhedral bilayer vesicles. In agreement with experiments, and provided that
excess amphiphiles exhibiting spontaneous curvature are present in sufficient
quantity, we find that polyhedral bilayer vesicles can indeed be energetically
favorable compared to spherical bilayer vesicles. Consistent with experimental
observations we also find that the bending energy associated with the vertices
of bilayer polyhedra can be locally reduced through the formation of pores.
However, the stabilization of polyhedral bilayer vesicles over spherical
bilayer vesicles relies crucially on molecular segregation of excess
amphiphiles along the ridges rather than the vertices of bilayer polyhedra.
Furthermore, our analysis implies that, contrary to what has been suggested on
the basis of experiments, the icosahedron does not minimize elastic bending
energy among arbitrary polyhedral shapes and sizes. Instead, we find that, for
large polyhedron sizes, the snub dodecahedron and the snub cube both have lower
total bending energies than the icosahedron