Papaioannou was born in the 1880s in Kolešino, then Ottoman Empire (now Republic of North Macedonia) and was a Slavophone Patriarchist with strong Greek consciousness.

He initially worked as a secretary of Boris Sarafov until 1903, but after realizing the real purposes of IMRO towards the Greek population, he travelled to Athens where he received military training.

Papaioannou and the majority of his armed group were killed in action on 8 September 1907 after the betrayal which lead to a battle against a large Ottoman army detachment.

[1][5] This made his cousin Charalambos Boufidis or from then known by the nom de guerre Kapetan Fourtounas join the struggle and avenge his death, acting against the Bulgarian Komitadjis and finally killing Peche who had betrayed Papaioannou.

His death led to a surge in local Greeks of his home region to join the struggle.