A simple nondestructive diffraction method is introduced to estimate the internal electric field present in the congruent lithium niobate crystal. Due to the presence of an unrelaxed internal field, the as-poled sample acts as an index grating and diffracts the incident light beam. By analyzing the diffraction patterns, we calculated the refractive index difference (
Δ
n
=
1.52
×
10
−
4
) between the poled and the unpoled domains, and the duty cycle error of 7.9%. Using the Pockels effect, the internal field
E
i
present in the periodically poled lithium niobate crystal is estimated to be 2.56 kV/mm.