Mountain Longleaf NWR is located within the Southern Appalachian Mountains between Atlanta, Georgia (90 miles) and Birmingham, Alabama (60 miles). The City of Anniston, Alabama is located adjacent to the refuge.

The refuge is situated along the rugged landscape of Choccolocco Mountain, one of the highest mountain ridges in Alabama. High elevation vistas (2063 feet ASL) provide an array of beautiful fall colors and breathtaking views of the surrounding region. Hardwood forests along mountain ridges contain species typical of the Blue Ridge Mountains to the north, while slopes and lower elevations are covered by longleaf pine and hardwoods commonly associated with the Coastal Plain.

The refuge was established on the former Fort McClellan military installation in 2003. Protection and management of old-growth and second-growth longleaf pine forests were the primary purposes for establishing the new refuge. Only in northwest Alabama and northeast Georgia do longleaf pine forests extend north of the Coastal Plain into the Appalachian Mountains. In recent years, this area has collectively become known as the Mountain Longleaf Pine Region.

A hundred years of army wildfires have maintained healthy longleaf pine forests over much of the refuge. Without recurring fire, these same forests have disappeared from much of the surrounding region. The refuge provides a unique laboratory for studying and understanding the natural composition of fire maintained second and old-growth longleaf pine forests.

The ecological importance of the refuge is clearly related to its' geographical location on a southern outlier of the Blue Ridge Mountains. The Southern Appalachian region is believed to support the most biologically rich temperate forest in the world. This narrow southerly extension of the Blue Ridge is sandwiched between the Ridge and Valley to the west and the Piedmont to the east. While the juncture of three physiographic provinces can be expected to provide varied avenues for complex plant and animal associations, a second and somewhat poorly understood environmental condition also exists. Longleaf pine, a forest community of the Coastal Plain, extends through the Piedmont, and deeply into the mountains of the Blue Ridge. The diversity of herbaceous plants in the ground cover makes longleaf pine forests among the most species-rich plant communities outside the Tropics. This forest community introduces decidedly southern species deep into the Appalachian Region.

The refuge can be described as containing characteristic Appalachian or northern community types on upper elevations and along ridgetops, with southerly, Coastal Plain, longleaf pine communities on the slopes. Along with this mosaic of overlapping natural communities come complex associations and transition communities, containing species common to both northern and southern regions.

Animals are often closely associated with specific plant communities and can also be expected to reach down from the Appalachians and up from the Coastal Plain. Some noteworthy Appalachian species known or suspected on the refuge include Appalachian cottontail, wood frog, scarlet tanager, ovenbird and worm-eating warbler.

During the early 1800s, Creek Indians lived in small villages along major rivers and tributary streams in northeast Alabama. The surrounding mountains were considered inhospitable and provided few benefits other than for hunting and food gathering. European settlers came into the region in the 1830s and continued to view the mountains primarily as a wasteland. The development of Anniston's iron industry in the 1870s, however, changed the importance of the mountains overnight. Mines were dug in mountainsides and the expansive longleaf pine forests were cut to fuel the iron furnaces. By the 1890s, the day of charcoal iron had passed and the mountains again returned to their solitude. In 1898 the Army recognized the training potential on these lands and eventually established Camp McClellan in 1917. Until closure in 1998, Choccolocco Mountain was owned and used to train military personnel for two World Wars, and the Korean and Vietnam Campaigns. Wildfires started through training activities inadvertently were responsible for the salvation of remnant longleaf pine forests on these lands.