Over the past decades, polymer mechanochemistry has focused on the development and application of advanced force application methods to better understand the mechanochemical response of mechanophores. In this regard, techniques such as ultrasonication and single-molecule force spectroscopy (SMFS) are used to activate and detect up to thousands of chemical events within a polymer single chain, allowing the researchers to probe the mechanochemical reactivity of these stress-responsive motifs. Here, the most recent contributions of the single-molecule force spectroscopy technique to this field are presented, putting emphasis on the fundamental parameters of the technique for triggering specific force responses and on the description of force-extension curves measured for single- and multi-mechanophore polymers. Moreover, new contributions of microscopy-based techniques in the field of polymer mechanochemistry, as well as the potential application of single-chain nanoparticles as mechanoresponsive materials, are highlighted.