In order to insure the success of the Christian missions among the pagan Wends (a Slavic people), Otto I suggested at the Roman Synod of 962 the creation of an archiepiscopal see at Magdeburg.

Pope John XII consented, and shortly before the execution of the plan in 968 it was decided at the Synod of Ravenna (967) to create three bishoprics — Meissen, Merseburg, and Zeitz — as suffragans of the Archdiocese of Magdeburg.

In 1346 the diocese stretched from the Ore Mountains and Iser Mountains in the south, from there northwards downstream the Queis and Bober rivers, forming the eastern boundary, in the north downstream the Oder to the junction of the Lusatian Neisse and on along the Oder, then crossing to the middle course of the Spree in the northwest, thus including Upper Lusatia (then the deanery of Bautzen) and Lower Lusatia (a provostry of the same name).

In the 13th century the pagan Wends were finally converted to Christianity, chiefly through the efforts of the great Cistercian monasteries, the most important of which were Dobrilugk and Neuzelle.

John VII of Schleinitz (1518–1537) was a resolute opponent of Martin Luther, whose revolt began in neighbouring Wittenberg (then part of the Diocese of Brandenburg), and, conjointly with George of Saxony, endeavored to crush the innovations.

John VIII of Maltitz (1537–1549) and Nicholas II of Carlowitz (1549–1555) were unable to withstand the ever-spreading Reformation, which after the death of Duke George (1539) triumphed in the Saxon part of the diocese.

The last bishop, John of Haugwitz (1555–1581), placed his resignation in the hands of the cathedral chapter, in virtue of an agreement with Elector Augustus of Saxony, went over to Lutheranism, married and retired to the castle of Ruhetal near Mögeln.

Before his resignation and conversion Haugwitz appointed Johannes Leisentritt as diocesan administrator, seated in Bautzen, competent for the Lusatian areas of the diocese outside of Saxony.

However, in 1567 the Holy See separated the Lusatian areas from the Saxon parts of the diocese and established there the Apostolic Prefecture of Meissen, seated in Bautzen, with Leisentritt as its first prefect.

When in 1635 the Lutheran Electorate of Saxony annexed the Two Lusatias it guaranteed in the cession contract (Traditionsrezess) with Bohemia to leave the existing religious relations untouched.

Prince-Bishop Emmanuel von Schimonsky combatted the rationalistic tendencies which were rife among his clergy in regard to celibacy and the use of Latin in the church services and ceremonies.

Pope Leo XIII appointed as his successor in the disordered diocese Robert Herzog (1882–1886), who had been before the Prince-Episcopal Delegate for Brandenburg and Pomerania and provost of St. Hedwig's in Berlin.

Prince-Bishop Herzog made every endeavour to bring order out of the confusion into which the quarrel with the State during the immediately preceding years had thrown the affairs of the diocese.

According to the census of 1 December 1905, the German part of the Breslau diocesan area, including the prince-episcopal delegation, comprised 3,342,221 Catholics; 8,737,746 Protestants; and 204,749 Jews.

On 21 June 1945 Bertram, while staying in the episcopal Jánský Vrch Castle in Czechoslovakian Javorník, appointed František Onderek (1888–1962) as vicar general for the Czechoslovak part of the archdiocese.

On 16 July the archdiocesan cathedral chapter, still comprising nine members, elected the Polish-speaking Ferdinand Piontek as capitular vicar, whom the Gestapo had banned from Breslau in early February 1945.

On 28 June 1972, however, – in response to West Germany's change in Ostpolitik – Pope Paul VI redrew the archdiocesan boundary along the post-war borders.