Lattice constants of sodium chlorate and sodium bromate and their mixed crystals were determined over the temperature range from room temperature to 320 "C. The observed lattice constants for the various compositions show strong deviations from those expected from Vegard's rule. The lattice constants at various temperatures were fitted to p l ynomials of type a = a,. + a,t + u,t2. The linear coefficients of expansion for the Na(ClO,), * * (Br0,)l --z series varies non-linearly with composition showing negative deviations from linearity.