The Curie temperature, birefringence, and phase‐matching temperature of LiNbO3are shown to vary with the stoichiometry of the melt from which the crystals are pulled. The range of melt stoichiometry, indexed by the Li/Nb mole ratio, was varied from 1.20 to 0.80. This Li/Nb variation changes the Curie temperature, refractive index for the extraordinary ray, and the phase‐matching temperature by 120°C,.03, and 320°C respectively. The relevance of these changes are discussed in terms of the susceptibility of LiNbO3to index inhomogeneities.