Matov was born in 1872 in Struga, Ottoman Empire (today part of the Republic of North Macedonia).
In 1895, while in Salonica, Matov was initiated into the Internal Macedonian Revolutionary Organization (IMRO) by Damyan Gruev.
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.
The failure of the Ilinden Uprising in 1903 reignited the rivalries between the varying factions of the Macedonian revolutionary movement.
He escaped assassination in 1907, when Boris Sarafov and Ivan Garvanov were killed by the leftist Todor Panitsa.