She started her music career in 1992. A year later she moved to Athens, Greece, where she had a cooperation with Yiannis Parios. Olympiou has also cooperated with other Greek music artists, including Haris Alexiou, Michalis Hatzigiannis, Dimitris Mitropanos, Mimis Plessas, Pandelis Thalassinos and Marios Tokas. She first appeared on the George Sarri album Ftaine oi Aponoi Kairoi with the song "I kounia mas". Olympiou also appeared on the album Emeis oi Ellines with the song "Pros rakosillektes kai sinodiporous" and on the Pandelis Thalassinos album Ap' tin Tilo os tin Thraki with four songs. Olympiou's first album, Ton Mation sou i Kalimera, includes music by Pandelis Thalassinos, Manoli Lidaki, Gerasimos Andreatos.
2002–2006: Universal Music, ''Vale Mousiki'', ''Exoume Logo'' and ''Auto Ine Agapi''
In 2002, she signed to the Universal Greece label. In June 2003, Olympiou started her cooperation with Michalis Hatzigiannis with the CD singleVale Mousiki with music by Hatzigiannis and lyrics by Eleana Vrachali. The album included a duet with Hatzigiannis, "Na 'soun allios", which was very successful. A year later the CD became platinum. A year later, she released her second album with the name Exoume Logo. In 2005, Olympiou released her new album, Auto ine Agapi, including twelve songs written by Giorgos and Alexandros Pantelia, apart from one song which was written by Lina Dimopoulou. The first single from the album was "Kapote".
2007–2012: ''Pes to Dinata'', ''Mazi Xorista'', ''Mia stigmi''
In the spring of 2007, she released the CD single Pes to Dinata, which was very successful both in Greece and Cyprus. Later Olympiou released her album, Mazi Xorista once again cooperating with Michalis, with lyrics by Eleana Vrachali and Nikos Moraitis. The album was re-released in 2008, this time gold, and includes the song "Pes to Dinata", "Mazi Xorista" and her duet with Michalis Hatzigiannis, "O Paradisos ". The album also includes the new song "Omorfa Psemata", written by Michalis Hatzigiannis and Nikos Moraitis. At the 2008 MAD Video Music Awards, she won the Best Duet award for the song "O Paradisos". In 2010, she releases her album entitled 'Mia stigmi', which became one of the most successful albums of that year, reaching Gold status in Cyprus. Considered as the most mature work by Despina, again penned by Michalis Hatzigiannis, included many hit singles like 'Pano stin agapi' which became a huge summer hit, 'Adynamia' and a very sentimental ballad entitled 'Mi m'agapas'. In 2012, Despina collaborated with Stereo Mike on a new hit single entitled 'Den s' afino apo ta matia mou', a duet that met great success in Cyprus and Greece, and marked her first steps without Michalis Hatzigiannis on her side.
On 1 February 2013, Cyprus Broadcasting Corporation announced that Olympiou had been internally selected to represent Cyprus in the Eurovision Song Contest 2013, held in Malmö, Sweden. On 14 February, the Greek language song "An me thimasai" was presented as the Cypriot Contest entry. An English acoustic version and Spanish version were also prepared for promotional purposes. Olympiou competed in the first semi-final of the Contest on 14 May 2013, however, she failed to qualify to the final, getting the fifteenth place with eleven points. Stereo Mike, the singer who Olympiou collaborated with on "Den s'afino apo ta matia mou", had also represented Greece in the Eurovision Song Contest 2011, held in Düsseldorf, Germany, along with Loukas Giorkas, with the song "Watch My Dance".
