The invention discloses a library robot intelligent three-dimensional (3D) navigation and putaway system based on a radio frequency identification devices (RFID) technology. The system comprises a book information reading module, a book information display module, a book putaway path generating module, an indoor positioning module, an automatic putaway module and a data storage module. The book information reading module comprises an internal information reading module and an external information reading module; the internal information reading module reads book RFID labels of books to be put on shelves, extracts book information through a background database server and displays the book information on the book information display module; the indoor positioning module displays the position of the system in a library in real time on the book information display module; and the book putaway path generating module generates a putaway path of books in an internal book-placing unit according to bookshelf position information of the books and position information of the positioning module and displays the putaway path to the book information display module. The automatic putaway module navigates the system to the putaway position according to the path generated by the book putaway path generating module.