We report optical spectroscopic measurements of molecular positronium (Ps(2)), performed via a previously unobserved L=1 excited state. Ps(2) molecules created in a porous silica film, and also in vacuum from an Al(111) crystal, were resonantly excited and then photoionized by pulsed lasers, providing conclusive evidence for the production of this molecular matter-antimatter system and its excited state. Future experiments making use of the photoionized vacuum L=1 Ps(2) could provide a source of Ps(+) ions, as well as other multipositronic systems, such as Ps(2)H(-) or Ps(2)O.