Puig will work alongside former IR chief Javier Zuloaga, now communications director, to manage a 20 strong team in Barcelona. She reports to Chairman Ricardo Fornesa and general manager Isidro Faine, according to media relations director Maria Luisa Martinez.
Formerly head of comms at La Caixa-owned water company Agbar, Puig is a long-term associate of Fornesa.
The appointment comes at a time of growing rumours about the bank's intention to lead a mega-merger between its top holdings Spanish-Argentine oil group Resol-YPF and Gas Natural, Spain's biggest gas supplier. The potential deal is seen as a precursor to a merger with power company Endesa, which would create a European energy colossus.