The German architect Leo von Klenze drafted the plans for the cathedral at the behest of King Otto of Greece.
During the project, the plans were modified by the Greek architect Lysandros Kaftanzoglou, who offered to direct the work of the church, until completion, without any remuneration.
Of the most beautiful is the fresco of semi-domes of triumphal arch, representing the Apotheosis of Saint Dionysius the Areopagite (1890) and is the work of Italian painter from Rimini Guglielmo Bilancioni (1836–1907).
Right and left of the main entrance are two inscriptions, one in Latin, the other in modern Greek, commemorating the Athenian visit of pope John Paul II in 2001.
In 1962, the Catholic marriage of Princess Sophia of Greece and Denmark and Infante Juan Carlos of Spain took place in the church, which preceded the Orthodox wedding rites.