Abstract: The Mössbauer spectra of Ni42CrTi Elinvar alloy in quenching, aged and cold-working states are measured respectively. On the basis of the spectra, the distributions of internal fields are calculated. The experimental P(H) curves spread widely and are decomposed into three Gaussian curves, which represent three preferential configurations of iron atoms. The variation in internal fields can be referred to the precipitation of γ' phase in the alloys, which results in the variation in the neighbouring environment of iron atoms. Comparing the relative areas under the probability peaks at different internal fields in P(H) curves, the relative amounts of γ phases in different states of alloys can be deduced. In addition, the intensity ratio of the components of Mössbauer spectrum indicates the extent of preferential orientation of magnetic moments.