Liani was born on April 30, 1955, in Florina, western Macedonia, Greece and is first cousin to former Iraklis footballer and Deputy Minister for Athletics, Giorgos Lianis. She had previously been married to Alexis Kapopoulos with whom she had co-hosted a short-lived television program called "Μισό-μισό" (Half and half).
Her relationship with the PM had caused controversy as Papandreou was already married to his second wife, Margaret Papandreou, when they met. Further controversy was caused when sexually compromising photos of Liani appeared in some Athens dailies. This, however, did not prevent Papandreou from including Liani in state functions - even before they were married - or going ahead with the marriage, even with opposition from his children.