Polysyllabic words have many syllables. The word librarian is polysyllabic, but the word book is not.
You can use the polysyllabic word polysyllabic for a word with more than one syllable, but it generally refers to words with more than three, like hippopotamus and misunderstanding. Sometimes people also describe long speeches or books full of unnecessarily big words as polysyllabic: "I got very sleepy listening to his polysyllabic lecture on philosophy." The Greek roots of this word are poly-, "many," and syllabe, "a syllable."