An overview of modern material science problems is presented for ultralightweight high-modulus commercial Al-Li-based alloys in historical retrospect. Numerous particular examples of the Soviet and Russian aviation whose various designs were made of these alloys confirm their successful innovative potential. The key regularities of multicomponent alloying are discussed for the master alloys and modern commercial Al-Li-based alloys of the latest generation; the features typical of their microstructures, phase composition, and properties formed during aging are analyzed. The main mechanisms of phase formation are generalized for standard thermal and thermomechanical treatments. Recent original achievements have been obtained in designing of unique structural and phase transformations in these commercial alloys by means of methods of severe plastic deformations followed by heat treatment and storage. Using the example of three Russian commercial alloys of last generation, the basic principles of creating and controlling an ultrafine-grained structure, the origin and growth of stable nanophases of various types and chemical composition that determine the physicomechanical properties of alloys are established.