The theory of electron spin-rotational (SR) relaxation in systems with an effective spin S-eff = 1/2 is formulated in terms of the adiabatic rotation of effective spin (ARES) approach. It is shown that SR relaxation results from the orientational random walk of the axes of the intramolecular electric field potential (ligand field) to which a spin-bearing atomic center is exposed. The validity of the stochastic treatment presented here is not limited by the Redfield conditions. The general expression obtained for the time constant of electron spin relaxation in liquid phase reproduces the well-known result of Hubbard-Atkins-Kivelson theory if it is specialized to the case of systems with weak spin-orbit coupling.