Like many late pre-dreadnought designs, Liberté was completed after the revolutionary British battleship HMS Dreadnought had entered service, rendering her obsolescent.

She immediately began the normal peacetime training routine of squadron and fleet maneuvers and cruises to various ports in the Mediterranean.

An investigation revealed that the standard French propellant, Poudre B, was prone to decomposition that rendered it very unstable; it had likely been the culprit in several other ammunition fires in other ships.

The engines were rated at 17,500 metric horsepower (17,300 ihp; 12,900 kW) and were intended to give the ship a speed of 18 knots (33 km/h; 21 mph).

[3] Coal storage amounted to 1,800 t (1,772 long tons), which provided a maximum range of 8,400 nautical miles (15,600 km; 9,700 mi) at a cruising speed of 10 knots (19 km/h; 12 mph).

[2] Liberté's main battery consisted of four 305 mm (12 in) Modèle 1893/96 guns mounted in two twin-gun turrets, one forward and one aft of the superstructure.

Her secondary armament consisted of ten 194 mm (7.6 in) Modèle 1902 guns; six were mounted in single turrets, and four in casemates in the hull.

The ships then steamed north to La Pallice, where they conducted tests with their wireless telegraphy sets and shooting training in Quiberon Bay.

The fleet returned to Toulon on 29 April, where Fallières doubled the crews' rations and suspended any punishments to thank the men for their performance.

The ships of 1st Squadron and the armored cruisers Ernest Renan and Léon Gambetta went on a cruise in the western Mediterranean in May and June, visiting a number of ports including Cagliari, Bizerte, Bône, Philippeville, Algiers, and Bougie.

[11] At 05:31 on the morning of 25 September, crewmen in other battleships reported seeing smoke coming from Liberté, originating from her forward starboard casemate.

Shortly thereafter, the forward superstructure erupted in flames, but it quickly appeared to observers that the ship's crew was getting the fire under control.

[12] The explosion threw a 37-metric-ton (36-long-ton) chunk of armor plate from the ship into the battleship République moored some 210 m (690 ft) away, which caused significant damage.

The investigation determined that the accident was likely caused by excessive heat in the magazines and deemed that the standard procedures for ammunition monitoring were not sufficient.

[12] The French Navy had earlier suffered a series of fatal accidents in Toulon, beginning with an explosion aboard a torpedo boat in February 1907 in which nine men were killed.

The wreck of the ship remained in Toulon for several years, though work on clearing or marking navigational hazards began immediately.

The shattered wreck had begun to sink into the mud by 1920, and so extensive work had to be done to prepare it to be refloated, including sending divers to build cofferdams to seal the hull.

On 4 September 1920, the old cruiser Latouche-Tréville was fitted with four and later six compressed air pumps and brought alongside to serve as a barracks for the workers and a floating workshop.