It must be noted that Athena forbids her warriors from using weapons. However, if justice is threatened, the Libra Saint can judge if the use of his Cloth's weapons is necessary.
Thus, Dōko fights mostly with his cosmo, using (or doning) only his weapons when there is no other way to defeat the enemy.
Shiryū used the Sword of Libra to free Hyoga from Camus' Freezing Coffin.
The Bronze Saints used Libra's weapons to destroy the Seven Ocean Pillars in Atlantis.
The Gold Saints used those weapons to try to destroy the Wailing Wall, albeit with no effect.
In The Lost Canvas, Dōko used the Trident of Libra to attack Hades, and the Libra Sword to fight Minotauros Gordon.
Ryūhō used the Libra Sword to break the Water Ruins
Genbu used the Libra Sword with his technique "Rozan Shō Ten Ha" to fight Aegir equipped with Hyperion's Tenchihōmetsuzan.
In the story of Saint Seiya many Saints use the Libra Weapon.