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In May of 1847, Bishop Blanc invited the Sisters of the Sacred Heart to Natchitoches to open a school.  The Bullard Mansion, the three columns which are now the symbol for Northwestern State University, was purchased for use as a convent.  In May of 1848, the Sisters bought a house adjoining the property and established a day school.  In 1850, the Sisters purchased a two-story house at the location of the old St. Mary’s on the hill on rue Touline.  In 1850, ninety children attended school at St. Mary’s.  The Sacred Heart Nuns remained in Natchitoches until 1876 and were replaced by the Sisters of Mercy, who remained in Natchitoches until 1879. 

In 1850, the Archdiocese of New Orleans was created.  In 1853, Natchitoches became a Diocese and the church’s name was changed to St. Mary’s.  The first bishop of Natchitoches was Father Augustus Martin.  Bishop Martin was consecrated on November 30, 1853 and installed on December 11, 1853.  At this time, there were six parishes in the Natchitoches Dicoese, one school, twenty-five thousand Cahtolics, twenty-two thousand square miles and four priest to serve the entire area.  In 1855, a seminary was built in Natchitoches, which was used until 1878.  This building is used today as the Bishop Martin Museum. 

In 1888, Mother General M. Florence sent five sisters to Natchitoches, where they arrived on August 29, 1888.  Three of the sisters taught at St. Mary’s Academy and the other two at St. Francis, a school established by Bishop Durier for people of color.  St.Mary’s Academy was housed in the former Placide Bossier House, which was previously used by the Sacred Heart Order and was located on a hill between rue Touline and rue Church.  In 1896, a new convent, which was a wooden, two-story house that contained galleries on two sides, was constructed. The first floor included a chapel and apartments for the sisters and borders while the second floor was used as the girls’ school and auditorium.  The boys school was established in the former St. Joseph College building, which originally had been the Placide Bossier House.

By 1907, the student population at St. Mary’s Academy had increased to 185 students, with nine boarders and seventy-six students of black or mixed race.  The students were taught by nine sisters.  In 1907, a two-story brick veneer building was constructed on the school grounds.  A story on the building’s dedication was included in The Family Circular, a journal written by a member of the Order, who was staffed at each of its educational institutions.

In 1948, St. Mary’s High School was moved to the former Natchitoches High School on rue Third while St. Mary’s Academy, which consisted of the grade school and junior high, remained at its original buildings.  By 1963, the facilities at both buildings were overcrowded and deteriorating.  In response, Father Donald Damieus, under the administration of Father Stanley J. DeKeuer, proposed the establishment of a new school building. 

Judge R.B. and Ora Williams, in memory of Eliza Payne Williams, donated 8.9 acres in east Natchitoches to construct a new school.  The Charles Maggio family, in memory of Mrs. Carmelite Maggio, donated 1.5 acres to the church parish and sold an additional 6.4 acres.  In 1967, the new school was erected and on May 13, 1967, the school was dedicated by Bishop Charles P. Greco.  The Sisters of Divine Providence remained teaching at St. Mary’s until 1971, when they returned to San Antonio.