Using differential x-ray absorption spectroscopy (DiffXAS) we have measured and quantified the intrinsic, atomic-scale magnetostriction of Fe81Ga19. By exploiting the chemical selectivity of DiffXAS, the Fe and Ga local environments have been assessed individually. The enhanced magnetostriction induced by the addition of Ga to Fe was found to originate from the Ga environment, where lambda;{gamma,2}( approximately (3/2)lambda_{100}) is 390+/-40 ppm. In this environment, 001 Ga-Ga pair defects were found to exist, which mediate the magnetostriction by inducing large strains in the surrounding Ga-Fe bonds. For the first time, intrinsic, chemically selective magnetostrictive strain has been measured and quantified at the atomic level, allowing true comparison with theory.