After earning his first Classics degree at Cambridge University, he returned to Greece in 1949–1950 as a member of the British School at Athens.
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He spent 1964–1966 as Visiting Fellow at Dumbarton Oaks, and was then Senior Lecturer and Reader in Byzantine History, Edinburgh University (1966–1970).
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For his contributions to the history of medieval Epirus, the city of Arta made him an honorary citizen in 1990, and he was awarded an honorary doctorate by the University of Ioannina in 1997.
Some authors (Donald Nicol and D. Polemis) have equated him with another John Petraliphas, who was a megas chartoularios in the employ of the Empire of Nicaea circa 1237, but this identification is most likely false.
The Byzantinist Donald Nicol, who researched the family's history, categorically identifies him as the brother of George Palaiologos Kantakouzenos; Giovanni Musachi makes him the brother of Irene Kantakouzene, wife of Serbian Despot Đurađ Branković, but incorrectly states Thomas was the son of the Emperor John VI Kantakouzenos, an error DuCange repeats.
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Syrgiannes's ambition, inveterate plotting, and multiple betrayals made him one of the darkest figures of the era in the eyes of both contemporary and later historians: the 14th-century historian Nikephoros Gregoras compared his flight to Serbia with Themistocles's flight to the Persians, while Donald Nicol likened him to Alcibiades and Angeliki Laiou called him "the most evil presence" of the civil war.