Samiou was born in 1928 in the Kaisariani neighbourhood of Athens, to a family of Greek immigrants from Asia Minor. At the age of thirteen, she began studying Byzantine and traditional music with musicologist Simon Karas, at the Association for the Dissemination of National Music.
As a member of the Simon Karas choir, she collaborated with the National Radio Foundation (E.I.R.), by which she was later hired at the National Music Section in 1954, thus being given the opportunity to be acquainted with the country’s leading traditional musicians.
While working for E.I.R., she did music editing for records, theatre productions, and films and, in 1963, began travelling around Greece, collecting and recording musical material for her own personal archives.
In 1971, Samiou resigned from EIR and, later in the year, accepted an invitation by singer - composer Dionysis Savvopoulos to start performe traditional songs before a young anti-junta audience. She later performed at the Bach Festival in London.
In 1976-77, she toured the Greek countryside and produced twenty episodes for the programme Musical Travelogue with Domna Samiou for Greek National Television (ERT). In 1981, the Domna Samiou Greek Folk Music Association was founded to preserve and promote Greek traditional music. Domna Samiou's work reaches beyond Greek borders. Her records have also been produced under French and Swedish labels. For more than 40 years, she had performed all over the world, appealing not only to the Greek Diaspora, but also introducing non-Greek audiences to 'Greek music with no Bouzouki', as one critic in Sweden eloquently put it.
She has been honoured and awarded with numerous rizes, including a medal from the President of the Hellenic Republic Kostis Stefanopoulos in 2005.