Aside from its technological importance, the Al-Li alloy system also exhibits interesting phase transformations involving both equilibrium and metastable states. Recent theoretical studies have shown that a supersaturated solid solution could take different transformation paths when it is quenched into the α +γ′ field. Suggestions were made that a rapidly quenched solution phase should first undergo a congruent ordering transformation before it decomposes into a two-phase mixture by either a secondary spinodal decomposition or the classical nucleation and growth process. Moreover, a metastable miscibility gap was predicted at lower temperatures. The objective of this research is to study the transformation paths and dynamics in Al-Li binary alloys of three compositions (5.2, 7.0, and 12.0 at. pct Li). This investigation emphasizes the in situ small-angle X-ray scattering (SAXS) observations on specimens subjected to various aging conditions. Special attention is paid to the early stages of the transformation in an attempt to characterize the various possible modes of phase separation on one hand and to study the dynamics of the precipitation process on the other. The following results are obtained: the congruent ordering precedes decomposition at low temperatures; the metastable γ′ solvus curve is reconfirmed; but the predicted metastable miscibility gap is not found. Guinier radii measurements of the particles showed Ostwald ripening is quickly reached upon heating to the aging temperatures. Slowing down behavior is seen at aging temperatures close to the solvus boundary. Activation energies for Li diffusion were obtained using the modified Lifshitz, Slyozov, and Wagner (MLSW) model. A test of dynamical scaling behavior is carried out for the Al-12.0 at. pct Li alloy. © 1990 The Metallurgical of Society of AIME.