Formation enthalpies of (001) surfaces terminating ordered Ga0.5ln0.5P and GaAs0.5Sb0.5 alloys were calculated using the VFF model. For several ordered phases, chemically ordered surfaces were found to be stable against surface segregation. In particular, even phases unstable against bulk segregation may be terminated by a stable surface.PACS numbers: 68.65.+g, 68.60.Dv, 61.55.Hg Thermodynamic stability has recently been investigated theoretically for several ordered lattice-mismatched alloys [1][2][3][4]. It was found that both (001) and (111) lattice-mismatched monolayer superlattices (MSL's) are intrinsically unstable at T = 0, and should segregate into pure end compounds. The instability of these systems persists even when the epitaxial stabilization is taken into account. As it was shown in [1], the instability is due to the excess elastic energy of bonds distorted by the lattice misfit.In the above context, the unintentional growth of both (001) and (111) lattice-mismatched MSL's is unexplained. Epitaxial growth of these phases has been recently reported for several III-V alloys [5]. The most frequent form of ordering, reported for all systems investigated so far, is a (111)-oriented MSL. On the other hand, the theory indicates that this phase is more unstable than both the (100) MSL and the random phase. Its metastability was confirmed experimentally [7]. One should observe, however, that the previous theoretical approaches neglected active role of the surface processes in epitaxy.In particular, it was suggested [8] that the growth of an ordered epitaxial alloy originates in a 2D ordering of atoms at the surface during growth. This, in turn, may be driven by the stability of chemically ordered surfaces. To verify this possibility, we have investigated surface stability against 2D segregation at T = 0, which is given by the surface formation enthalpy (125)