Single molecule force spectroscopy (SMFS) is a powerful means in studying the intramolecular and intermolecular interactions in polymer and supramolecular systems, thus opening new horizons for nanomechanic chemistry. This feature article concerns mainly how to employ AFM-based SMFS to obtain some of the important information which is not available by conventional characterizing methods, including single chain mechanics, the interfacial conformation and adhesive energy of polymers, interaction between macromolecules and small molecules, and the direct measurement of intermolecular forces. In addition, some of the recent advances in using the SMFS to bottom-up assembly of functional nanostructure are also discussed. (C) 2008 Elsevier Ltd. All rights reserved.