Deques, as outlined in the Python standard library documentation, offer efficient, thread-safe operations for appending and popping elements from either end with O(1) complexity, making them more efficient than lists, especially for operations involving both ends. The text explores an example of rotating letters in a string, initially approached with a custom function using lists, but later optimized using the native rotate method of a deque, highlighting that deques also allow rotation to the left or right with a simple method call. The author emphasizes the importance of exploring standard library documentation and asking questions to enhance one's programming skills, noting that even casual exploration can lead to discovering more efficient methods and practices, such as the faster lookup times in sets or dictionaries compared to lists.