Spontaneous radiative association of the molecular ion LiHe+ is investigated including three electronic states X-1 Sigma(+); A(1)Sigma(+), and a(3)Sigma(+). Cross sections for four processes of radiative association X -> X, A -> A, A -> X, and a -> a are calculated as functions of collision energy. The corresponding rates of formation are derived as functions of temperature. The A -> X radiative association process exhibits the largest cross sections and rate coefficients because of the huge amount of the de-excitation energy from the A state to the X state. (C) 2012 Elsevier B.V. All rights reserved.