Consecrated to Saint Emperors Constantine and Helen, the church is situated on the Metropolitan Church Hill, and is a construction of impressive proportions (28 m long in the interior, with a 14.60 m wide narthex). It was raised in 1656-1658 by prince Constantin Serban Basarab. During Radu Leon's rule (1664-1669), the church became the Wallachian Metropolitan seat, as in the 16th century it had been moved from Târgoviste to the Sf.Gheorghe-Vechi Monastery first, and then to Radu Voda Monastery in Bucharest.

In a document dated 8 June 1668, prince Radu Leon states that "I painted and ornated it (the church) with all the adornments". The structure of the church - three-cusped, with an enlarged narthex, and four steeples above - reproduces almost faithfully the plan of the See Church at Curtea de Arges; however, its bigger dimensions and the large open porch supported by twelve brick pillars differentiate it from the latter.

The façades are decorated with two registers of blind arches, separated by a median stone belt made up of three mouldings twisted here and there. The blind arches in the lower register are simple, while those in the upper one are narrower and grouped in pairs. The median belt is set between two rows of bricks placed in a sawteeth pattern.

Out of the old 1668 frescoes, only the icon representing the patrons of the church was preserved and can be seen in the recess above the porch door. Above the porch, there are several paintings accomplished in 1935-1939 by D.Belizarie; they represent angels, prophets and the twelve Apostles. In the narthex there is the votive picture of Constantin Serban Basarab and Radu Leon with their wives, as well as the portraits of the Metropolitans who had the church restored or repaired, among whom Patriarch Miron Cristea. It is also in the narthex that stands a silver chest with relief ornaments, holding the relics of St.Dimitrie Basarobov - the saint patron of Bucharest - brought from Bulgaria by the Russian general Salticov, and presented as a gift to the Metropolitan Church.

The belfry in front of the church was raised in 1698 by Constantin Brâncoveanu, and was restored in 1958. The Metropolitan Church is the place where all official religious ceremonies are held.

In 1688, the printing workshop of the Metropolitan Church brought out the famous Bible of Bucharest, the first complete translation of the Bible into Romanian, made by brothers Serban and Radu Greceanu and issued on Serban Cantacuzino's initiative. This work, a monument of the old Romanian language, played an important role in the development of the literary Romanian language.

During the restoration works of 1799, 1834-1839, 1850 and 1886, the old paintings were effaced, and certain changes and completions were made. The most important repairs and restorations were carried out by the Commission for Historical Monuments in 1935-1939, and in 1959-1962, when the church was repainted and got an aspect close to its present one.