Lithium-excess binary clusters LinFn - 1 (n = 2-9) were detected by photoionization time-of-flight mass spectrometry in a supersonic cluster beam generated by a laser ablation of a solid mixture of Lithium fluoride and nitride. Laser power dependence of the Li2F+ signal intensity has indicated that the ionization energy of the hyperlithiated Li2F molecule is lower than 4.66 eV. The theoretical vertical ionization energy obtained by the CCSD(T)/6-311 + G(d)//B3LYP/6-311 + G(d) calculations are 4.47 eV. No nitrogen-containing clusters were detected. The absence of Li4N is ascribed to the exothermicity of the reaction, 2Li(3)N --> N-2 + Li-6.