In two previous papers [26,27], the exact solutions of the spin-12 chains with arbitrary boundary fields were constructed via the off-diagonal Bethe ansatz (ODBA). Here we introduce a method to approach the thermodynamic limit of those models. The key point is that at a sequence of degenerate points of the crossing parameter η=ηm, the off-diagonal Bethe ansatz equations (BAEs) can be reduced to the conventional ones. This allows us to extrapolate the formulae derived from the reduced BAEs to arbitrary η case with O(N−2) corrections in the thermodynamic limit N→∞. As an example, the surface energy of the XXZ spin chain model with arbitrary boundary magnetic fields is derived exactly. This approach can be generalized to all the ODBA solvable models.