In 1895, while in Salonica, Matov was initiated into the Internal Macedonian Revolutionary Organization (IMRO) by Damyan Gruev. His education warranted his subsequent appointment as a director of the Bulgarian pedagogical school of Skopje. In less than a year as head of the school, he succeeded in organizing many revolutionary committees. In 1898 he was elected as member of the Central Committee in Salonica.
In 1901, when the Salonica outrage occurred and the Ottoman authorities arrested many IMRO activists, he was imprisoned there and later exiled to Bodrum, Asia Minor. In 1902, as a result of a general amnesty, he was released and allowed to return to Thessaloniki. Soon after, he went to Sofia as a representative of the Central Committee of the IMRO.
The failure of the Ilinden Uprising in 1903 reignited the rivalries between the varying factions of the Macedonian revolutionary movement. The left-wing faction opposed Bulgarian nationalism but the Centralist's faction of the IMARO, drifted more and more towards it. At that time Matov became one of the leaders of the Centralist faction. He escaped assassination in 1907, when Boris Sarafov and Ivan Garvanov were killed by the leftist Todor Panitsa. Afterwards, he participated in the Balkan Wars and in the First World War as a Bulgarian officer.
Matov was acknowledged as a constitutionalist of the Macedonian movement. He is the author of several books, a number of pamphlets, and several poems while in prison.
^...Постоечките документи говорат дека таа била наречена „Бугарски македоно-одрински револуционерни комитети“. Оваа име Организацијата го добила на својот прв Конгрес одржан во летото (15 август 1894) во Ресен... Иван Катарџиев, Кон спомените на И.Х.Николов... Скопје 1995. стр. 8-9.
^Historical Dictionary of the Republic of Macedonia, Dimitar Bechev, Scarecrow Press, 2009, ISBN0810862956, p. 143.