Since 2002, the station has been part of the Upper Middle Rhine Valley UNESCO World Heritage site.

The Bonn-Cologne Railway Company opened its line between Cologne and Bonn in 1844, and extended it to Rolandseck in 1856.

On 11 November 1858, the first train, hauled by the locomotive Windsbraut ("whirlwind") ran over the newly built Moselle railway bridge on the Left Rhine line to a provisional station on Fischelstraße.

In 1879, the Moselle line was put into operation and its station (Moselbahnhof) was opened below Fort Konstantin, near the modern Hauptbahnhof.

The maintenance of two stations proved to be very complicated, because through trains had to stop twice within 900 m (3,000 ft) and passengers coming from Trier and wanting to travel on the right Rhine line to the north had to take a horse-drawn cab or walk between the Moselle and the Rhenish station.

The through station was built like a palace with central and side pavilions, although for functional reasons it was not completely symmetrical.

The northern wing of the royal room (Fürstenzimmer) was richly decorated and had direct access via a flight of stairs to platform 1, on which the Emperor arrived in Koblenz in 1905.

The station building and the railway tracks were damaged in air raids during the Second World War.

Regional services consist of Regional-Express and Regionalbahn trains to cities within 200 kilometres towards Saarbrücken, Cologne and the Ruhr, Emmerich / Wesel, Giessen and Mainz-Frankfurt am Main.