A newly developed real time spectral birefringence technique was implemented to follow the coupled relationships between birefringence, true stress and true strain behavior of varying crosslink density natural rubber vulcanizates at room temperature. It was shown that the stress optical law is valid even at early stages of crystallization during stretching and there exists a critical birefringence beyond which the metastable “near perfect” oriented and highly distorted crystalline regions form and upon retraction this crystalline order disappears at the same critical birefringence level. These crystalline regions exhibit nematic order with significant axial registry distortions at early stages of the formation. They are suggested to form at or near the juncture points of the chemical network formed by crosslinks, and physical network by chain entanglements where the orientability of the chains is the most efficient.