The College was established on October 6, 1884 and its first president, Commodore Stephen B. Luce, was given the old building of the Newport Asylum for the Poor to house it on Coaster's Harbor Island in Narragansett Bay. Among the first four faculty members were Tasker H. Bliss, a future Army Chief of Staff, James R. Soley, the first civilian faculty member and a future Assistant Secretary of the Navy, and most famously Captain (later, Rear Admiral) Alfred Thayer Mahan, who soon became renowned for the scope of his strategic thinking and influence on naval leaders worldwide. Despite Mahan's prestige, the College was long met with skepticism by Navy officers accustomed to conducting all education aboard ship.

The College engaged in wargaming various scenarios from 1887 on, and in time became a laboratory for the development of war plans. Nearly all of the U.S. naval operations of the twentieth century were originally designed and gamed at the NWC.

One of the most famous achievements of the NWC was the Global War Game, a large-scale wargaming effort to model possible United States-Soviet Union confrontation during the Cold War.

The current president is Rear Admiral James P. Wisecup, a native of Piqua, Ohio, and a 1977 graduate of the U.S. Naval Academy. He earned his Masters Degree in International Relations from the University of Southern California, is a 1998 graduate of the Naval War College, and he also earned a degree from University of Strasbourg, France, Institute for Advanced European Studies, as an Olmsted Scholar.

As of 2008, in response to military to demand for education on irregular warfare the NWC started the Center for Irregular Warfare and Armed Groups.

Its principal courses of study are "Strategy and Policy", "National Security and Decision Making", and "Joint Military Operations". Students from all branches of the military, as well as foreign militaries, work towards a Master of Arts.

The Naval War College has two international courses, Naval Command College (NCC) and Naval Staff College (NSC), specifically prepared for the naval officers of other nations. Graduates of these programs include numerous chiefs of the maritime forces all over the world.

Despite the extensive international presence, the Naval War College, unlike other U.S. military staff colleges, has never granted a master's degree to an officer of another nation.[citation needed] The Naval War College declines to grant degrees to its international graduates because some officers from other navies have no undergraduate credential, generally an essential requirement for conferring a master's degree in the United States.

The NWC Press has published a number of books, and has put out the quarterly Naval War College Review since 1948.

Over the years, the Naval War College has expanded greatly. The original building, the former Newport Asylum for the Poor, now serves as home to the Naval War College Museum. In 1892, the structure now known as Luce Hall opened as the college's new home, at a cost of $100,000. At the time, the building housed lecture rooms and a library. Wings at either end provided two sets of quarters, occupied by the president of the College and members of the faculty. When the Naval War College was enlarged in 1932, this original building was renamed Luce Hall in honor of the institution's founder and first Superintendent (later President), Stephen B. Luce. The building was entered onto the National Register of Historic Places on September 22, 1972.