Samuel Bell Maxey spent his early years in Tompkinsville, Monroe County, Kentucky. His family lived in nearby Clinton County when Maxey was appointed to United States Military Academy at West Point. Upon graduation in 1846, he was breveted a Second Lieutenant in the regular army and served in the Mexican War until its close in 1848. In 1849 he resigned from the United States Army and returned to his home in Clinton County, Kentucky, where he studied law under his father, Rice Maxey. In 1850 he entered law practice with his father and in 1857 they moved their families and business to Paris, Texas.

In 1862 Maxey was made a Brigadier General in the Confederate Army and served briefly in the Trans-Mississippi Department. In December, 1863, he was made Commander of the Indian Territory where he served until February, 1865.

As an attorney, Maxey became acquainted with many of the prominent lawyers and politicians of Texas. He traveled to Austin and other places over the state in order to conduct his legal business. He was acquainted with Richard Coke, James W. Throckmorton, Oran M. Roberts, Guy M. Bryan, John H. Reagan and others of political note in Texas. He maintained his acquaintance with his political friends in Kentucky, namely, Governor Preston J. Leslie and U. S. Attorney-General James Speed. The culmination of this period of Maxey's life came in 1874 when he was elected to the United States Senate.

Maxey was defeated for reelection in 1887. In 1888 he returned to his law practice in Paris, Texas, and spent his last years there. He had five law partners during his lifetime. They were Rice Maxey, William H. H. Long, Henry William Lightfoot, Ben H. Denton, and W. F. Gill. Samuel Bell Maxey's wife, Marilda, was the daughter of George N. Denton, a Baptist preacher and farmer of Overton County, Tennessee.

Dora Rowell Maxey was the daughter of Thomas Rowell of Florida. Her father was a Confederate soldier who died in the Civil War. She was left an orphan and was legally adopted in 1863 by Samuel Bell Maxey and his wife. She attended a girl's school in Danville, Kentucky, from 1872 to 1874. She married Henry William Lightfoot and had two children, Sallie Lee Lightfoot and Thomas Chenoweth Lightfoot.

Sam Bell Maxey Long, grandnephew and foster son of Samuel Bell Maxey, attended Schools in Washington, D. C., and was a page in the United States Senate, and later obtained a degree from the University of Texas in 1892. He accompanied Maxey to Washington in 1876 when he was a small boy and continued to do so for a number of years. He married Lala Williams, daughter of J. S. Sheb Williams.