We analyze a model for CO oxidation on surfaces which incorporates both rapid diffusion of adsorbed CO, and superlattice ordering of adsorbed immobile oxygen on a square lattice of adsorption sites. The superlattice ordering derives from an “eight-site adsorption rule,” wherein diatomic oxygen adsorbs dissociatively on diagonally adjacent empty sites, provided that none of the six additional neighboring sites are occupied by oxygen. A “hybrid” formalism is applied to implement the model. Highly mobile adsorbed CO is assumed randomly distributed on sites not occupied by oxygen (which is justified if one neglects CO–CO and CO–O adspecies interactions), and is thus treated within a mean-field framework. In contrast, the distribution of immobile adsorbed oxygen is treated within a lattice–gas framework. Exact master equations are presented for the model, together with some exact relationships for the coverages and reaction rate. A precise description of steady-state bifurcation behavior is provided utilizing both conventional and “constant-coverage ensemble” Monte Carlo simulations. This behavior is compared with predictions of a suitable analytic pair approximation derived from the master equations. The model exhibits the expected bistability, i.e., coexistence of highly reactive and relatively inactive states, which disappears at a cusp bifurcation. In addition, we show that the oxygen superlattice ordering produces a symmetry-breaking transition, and associated coarsening phenomena, not present in conventional Ziff–Gulari–Barshad-type reaction models.