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You learn to use Power Armor when you go to the Citadel the first time, although it is avoidable. When you first visit the Citadel, you will have to talk to the main Elder for his permission to be granted access to Power Armor training. Once you have it, go to see an instructor outside who will train you for no fee instantly. Alternativley you can play the 'Operation Anchorage' DLC pack and when you come out of it you will have the ability to wear Power Armor [this can be done as soon as you complete the 'Escape' quest at the begining of the game if you start a new save and have the DLC installed on your Xbox 360/PC so you don't have to wait too long to have the ability].