Predicting the compositional evolution of the atomic-scale structure of oxide glasses is important for developing quantitative composition property models. In binary phosphate glasses, the addition of network modifiers generally leads to depolymerization of the networks as described by the Q-speciation, where Q(n) denotes PO4 tetrahedra with n number (between 0 and 3) of bridging P-O-P linkages per tetrahedron. Upon the initial creation of nonbridging oxygens and thus partly depolymerized Q species, a variety of network former modifier interactions exist. Here, on the basis of P-31 magic angle spinning nuclear magnetic resonance spectroscopy data from the literature, we present a statistical description of the compositional evolution of Q-speciation in these glasses by accounting for the relative enthalpic and entropic contributions to the bonding preferences. We show that the entire glass structure evolution can be predicted based on experimental structural information for only a few glass compositions in each series. The model also captures the differences in bonding preferences in glasses with different field strengths (charge-to-size ratio) of the modifier cations.