The optogalvanic effect is proposed and demonstrated as a technique for Penning ionization in a discharge of mixtures of metal vapors and rare gases. The gadolinium and argon mixture is used as a prototype. The lowest metastable of argon, 3P$_2$ (ls$\_$5/ in Paschen notation) at 93144 cm$^$-1/, is within kT from the excited states of Gd ion. Thus Penning ionization occurs to an excited states of the ion. This process strongly alters the optogalvanic signal and has its own signatures.