Austin College was first established in 1849 through the efforts of local Presbyterians. The college was named for Stephen F. Austin, the "Father of Texas." Austin was the Secretary of State of the Republic of Texas and was responsible for bringing thousands of settlers from the United States to Texas when it was still a part of Mexico. Sam Houston and Anson Jones, past presidents of the former Republic of Texas, were charter members of the Austin College Board of Trustees

The original two-story Austin College building was constructed from 1851 to 1852 in the Greek-Classical style. In 1855, Austin College housed the first law school in Texas, and in 1876, Austin College moved to Sherman, Texas, due to the economic declines as a result of the Civil War, the Reconstruction, and the yellow fever epidemic of 1876. That same year, Standford Gibbs and fellow businessmen purchased the Austin College property to donate to the state.

Mitchell College was established in 1877 in the vacated Austin College Building, which the Methodist Church had purchased for $1,000, intending to use it as a school for boys. The effort failed within a year and it was sold back to the city of Huntsville for $346.

On April 21, 1879, Sam Houston Normal Institute (SHNI) was established on the property. SHNI was the first tax-supported teacher training institute in Texas and received a $2 million endowment from the Peabody Education Fund, which was created to develop and improve educational facilities in the South after the Civil War. On October 10, SHNI officially opened its doors to the first class of 110 students with four faculty members.

Until 1890, when the Main Building (also known as Old Main) was built, all SHNI classes were held within the Austin College Building, which came to be called as Austin Hall. Austin Hall continued to hold all biology and natural science classes until the Science Building (now the Bobby K. Marks Administration Building) was built in 1916. Austin Hall also functioned as a training school until the completion of the original Education Building in 1918. Also, for a brief time, from September to December 1918, Austin Hall was a dormitory for students in the Army Training Corps.

Due to a lack of space, a third floor was added to Austin Hall, with construction completed in 1882. The third floor was built in a French-Modern style, clashing with the Greek-Classical style of the rest of the building. The pre-existing copula and the Sam Houston Bell were removed and shipped to Sherman, TX. The third floor housed the library and classrooms, but over the years had various other functions, including the school chapel and an office space for the Houstonian, the school newspaper, and the Alcalde, the school yearbook. Due to a leaky roof, the third floor was removed in 1927 and a portico was added facing the newly developed campus.

Austin Hall was considered the social hub of SHNI (later called Sam Houston State Teachers College, Sam Houston State College, and Sam Houston State University) until 1950, when the Student Union Building (SUB) was built.

In 1964, Austin Hall was recognized and recorded as a Texas Historic Landmark, and in January 2, 2013, it was named to the National Register of Historic Places.

By 1982, the first floor housed alumni offices and a faculty reception area and the second floor housed the Department of Military Science and Reserve Officers' Training Corps (ROTC). When the Main building next door burned to the ground on February 12, 1982, Austin Hall's roof was severely damaged. Most of the furniture, equipment, ROTC files, and almost all archival materials were destroyed. The Department of Military Science and ROTC moved into Randel House. Austin Hall was restored with a cupola like the original and rededicated in October 1986.

Another lengthy restoration process for Austin Hall began in fall of 2011, made possible by donations from the Houston Endowment Inc., The Brown Foundation, The Elkins Foundation, alumni, and local businesses. The cost for the restoration was $2.2 million, which included floor refinishing, new electrical and plumbing systems, masonry work, and restoration of the roof, cupola, and shutters. In 2012, the restoration was completed and on October 12, a rededication ceremony held.

Austin Hall is currently used for special university events.

Austin Hall is the oldest building west of the Mississippi River to have been continuously used by an educational institution. It is the oldest building on the SHSU campus.