Today, Biebricher Allee begins west of the main railway station on Kaiser-Friedrich-Ring and leads south via Adolfshöhe to Herzogsplatz in Biebrich. One of the two old main connections between Wiesbaden and Biebrich originated from the limited "Alter Mosbacher Weg", which led from Mosbach, located to the north of Biebrich, via the "Hohl" (today's Weihergasse), its extension (today's Volkerstraße) and over the hill (today's Steinberger Straße) in the direction of Wiesbaden.

A few years after Prince Karl zu Nassau-Usingen had moved his residence from Usingen to Biebrich and the government to Wiesbaden, he had the "Neue Mosbacher Straße" built between 1749 and 1752 in the form of a wide country lane in order to create a direct route from Biebrich to the old Wiesbaden Palace for the court and government officials. This new path, which was not paved until 1808, already followed the current route of Biebricher Allee, but had a completely different character due to the neighboring fields and meadows. In 1854/55, the path was widened to its present width and given a firm surface. In 1856/57, a promenade path was laid out on the western side and a bridle path on the eastern side. The new Chaussee was planted with four rows of chestnut trees, which characterized the image of the avenue until the end of the 1970s. They were later replaced by lime trees and reduced to two rows due to traffic.

At the time of the new construction of the Chaussee, the road from Wiesbaden to Biebrich was undeveloped. Only at the entrance to Mosbach (today Gibb) were there two houses at the beginning of what is now Äppelallee, the inns "Zum Löwen" and "Zum Himmel". In 1856, Duke Adolph zu Nassau authorized the construction of a restaurant on the hill between Wiesbaden and Biebrich (at today's intersection of Biebricher Allee/Konrad-Adenauer-Ring), which was named "Adolph's Höhe" and thus gave its name to the villa district that was later built here.

The development of villas on the western side of the avenue, which began around 1870, was followed by the opening of the first steam streetcar in 1889, which ran from the banks of the Rhine in Biebrich to the Nero Valley. It was not until 1900 that the single-track steam tram line was replaced by a double-track electric streetcar, which ran until 1945. The Biebrich water tower, which was built in 1897 to the east of the avenue and served as a flood reservoir and observation tower, can be seen from afar. To the south of the water tower, there were sand pits on both sides of the avenue, filled with the famous Mosbach sands of diluvial (ice age) origin. After the death of Adolph zu Nassau in 1905, the town of Biebrich decided to use part of the space at the western sand pit for a monument in honor of the duke. The inauguration of the Nassau State Monument took place on October 26, 1909. A park was created in the western part, the Richard-Wagner-Anlage (today also known as Henkellpark), which was to offer spa guests and day-trippers a new attraction.

As early as 1907, the Henkell & Co. sparkling wine company, which was unable to find space in Mainz for the planned expansion of its production, was persuaded to settle in Biebrich. Production and storage facilities could be accommodated in the lower area of the site (the eastern sand pit). The reception building, designed by architect Paul Bonatz, was inaugurated in 1909 and is still a special gem on Biebricher Allee today. Also in 1907, the Landesdenkmal station was built next to the Henkell company in the direction of Wiesbaden as a stop on the Aartalbahn.

The First World War put an abrupt end to the lively building activity along Biebricher Allee. In 1929, an area to the west between Nassauer Straße and Normannenweg was made available for the construction of small homes.