Perraivos was born in 1773 in Pano Pourles near Mt Olympus. His family was originally from Perraivia, Thessaly. At age 20, he left Greece to study in Bucharest and Vienna. There, he met Rigas Feraios and became his friend and companion. Together they were arrested in Trieste in 1797 but, unlike Feraios, Perraivos was released thanks to the help of the local French consul. Afterwards he left for Kerkyra and enlisted in the French army. In 1817, he became a member of the Friendly Society (Filiki Eteria) which sought to unite all Greeks in anticipation of a war of independence against the Ottoman Empire.
After the outbreak of the war in 1821, Perraivos served as Minister of War in 1823 and General in 1825. He fought in several battles and was with Georgios Karaiskakis when the latter was killed in a skirmish at Neo Faliro.
After independence Perraivos authored his "Wartime Memoirs". In 1860, he also wrote a book about Rigas Feraios - "Rigas the Thessalian". Prior to the war he had written the "History of Souli and Parga".