The π 0 → γγ decay width is analyzed within the combined framework of Chiral Perturbation Theory and the 1/N c expansion up to O(p 6 ) and O(p 4 × 1/N c ) in the decay amplitude. The η ′ is explicitly included in the analysis. It is found that the decay width is enhanced by about 4.5% due to the isospin-breaking induced mixing of the pure U (3) states. This effect, which is of leading order in the low energy expansion, is shown to persist nearly unchanged at next to leading order.The chief prediction with its estimated uncertainty is Γ π 0 →γγ = 8.10 ± 0.08 eV. This prediction at the 1% level makes the upcomming precision measurement of the decay width even more urgent.Observations on the η and η ′ can also be made, especially about their mixing, which is shown to be significantly affected by next to leading order corrections.