In Athens, her first year of singing in the Athenian music clubs was with Peggy Zina. Soon after, she got a record contract with Minos EMI and released her debut album To Proto Vima (The First Step) in June 2003. Writers of the album included well established composers such as Evi Droutsa, Marios Psimopoulos, Christodoulos Siganos, and more. The songs “Mi M’Akoubas” and “Shedon Pote” became hits and showcased her talent, while the latter became the theme song for the series of the same name on ERT. In the summer of 2004, she started appearances at popular club “Thalassa” with Elena Paparizou, Thanos Petrelis, and Nino where she further showcased her vocal abilities.

After the summer of 2004, she left Minos EMI and signed with the newly created imprint Virus Music of the Greek independent record company Legend Recordings. In the fall of 2004, she started appearances at the club “Gazi” with Nikos Kourkoulis and Andreas Stamos. In January 2005, she released her second album under Virus titled Apo Do Kai Pera (From here on out). The single “Krima” written by Christos Dantis became a huge radio hit, and her first true big hit. The album produced many hits including “Mou Eleipses”, “Apo Do Kai Pera”, and “De Vazo Ego Mialo”, making her a household name.

On May 5, 2006, Apostolia Zoi released her third studio album titled “Th’ Afisei Epohi” (It will leave a history) featuring fifteen new songs. This album featured a bit of a different sound while not completely straying away from the sound of the first two albums. The titled track because a hit, while the album also featured a rap style duet with friend Gianni Tsimitseli titled “Lipstick”.

In June 2007, Zoi sang a duet remix with the famous Kostas Tournas of “Geia Sou” at the “Mad Music Video Awards”. For the winter season of 2007-2008, Zoi sang at “Kendro Athinon” with Giannis Ploutarhos, Tamta, and Giannis Vardis. In Fall 2007 she re-signed with her original record company Minos EMI. She then went into the studio to record new material for her fourth studio album. On June 9, 2008, Zoi released the first single “Ti stis 8, Ti stis 7” exclusively on Rythmos FM which was followed by the release of her fourth studio album Me To Heri Stin Kardia on June 23. The second single “Ki Esi Ekei”, was released in mid-September 2008 with lyrics by Ilias Fillipou and music by Giorgos Kafetzopoulou.