He was the son of the painter Luigi Postiglione. His elder brother, Salvatore Postiglione was also a painter and his teacher. Luigi's uncle, Raffaele (1818–1897) was a professor at the Neapolitan Institute of Fine Arts.
Among his works are L'orfana exhibited at the Italian Exhibition in London in 1904, while Il giglio, and La Soglia were exhibited at the International Exposition in Rome in 1906.
- Rendiconto della Accademia di archeologia, lettere e belle arti. (1907) By Accademia di archeologia, lettere e belle arti di Napoli, page 516.
- Artisti Napoletani Viventi: Pittori, scultori, incisori, ed Architetti. Enrico Gianelli, preface by Eduardo Dalbono. Tipografia Melfi e Joele, Naples, 1916, page 386-387.
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