The name "Panagia Chrysospiliotissa" has several different interpretations. According to one famous story, the name comes from the contribution of the Monastery of Mega Spileo in its construction, which was located near the present-day city of Thebes. The monastery was known for its rich collection of religious artefacts, including a replica of the icon of the Virgin Mary. It is believed that the icon was transferred to Athens and placed in the church, giving it the name "Chrysospiliotissa" or "Golden Cave."

Another interpretation of the name is that it refers to the church's location, which was built inside a cave-like structure that was once part of an ancient temple. The cave was said to have been the site of several miracles, including the appearance of the Virgin Mary to a group of shepherds. The church was built on the site to commemorate these events, and its name reflects the importance of the cave in the history of the church.

The construction of the church was a major undertaking, and it took several years and significant efforts by the residents of the area to complete. The first church, a basilica built in 1705, was destroyed during the siege of the Acropolis by Kütahı in 1826. In 1832, the erection of a new church began, but it proved too small for the needs of the area. In 1846, the residents bought nearby building plots and started raising funds to construct a larger church.

The church was designed by the famous architect Dimitrios Zezos, who is considered the person who introduced the "Greek-Byzantine" architectural style. However, Zezos died before the construction of the church began, and the supervision of the works was initially taken over by Panagis Kalkos and later by Ernst Ziller, who is believed to have designed the screen. The dome was the work of the architect Dimitrios Soutsos, Athens's mayor at the time.

The church is a magnificent example of the eclecticism style that was popular in the 19th century, combining neoclassical with Byzantine elements. Some of the notable features of the church include its intricate cloisonne masonry, double-light windows, and marble decorations. The church's interior decoration was completed in 1892 and was made by famous artists, including prominent painters, sculptors and iconographers.

Overall, the church of Panagia Chrysospiliotissa is a rich tapestry of history and art, reflecting the cultural and religious heritage of Athens. It remains an important place of worship and a symbol of the city's rich cultural heritage.