Recently, mechanical milling using a mixer mill or planetary mill has been fruitfully utilized in organic synthesis under solvent-free conditions. This review article provides a comprehensive overview of various solvent-free mechanochemical organic reactions, including metal-mediated or -catalyzed reactions, condensation reactions, nucleophilic additions, cascade reactions, Diels-Alder reactions, oxidations, reductions, halogenation/aminohalogenation, etc. The ball milling technique has also been applied to the synthesis of calixarenes, rotaxanes and cage compounds, asymmetric synthesis as well as the transformation of biologically active compounds.