Several methods for the preparation of the interesting and valuable compounds 3-alkyloxypivalic acids starting from substituted 1,3-dioxanes were examined. While one-step procedures combining isomerisation and oxidation were not successful due to degradation of formed intermediates and products, a two-step environmentally benign method could be established using O-2 as oxidant in the presence of heterogeneous catalysts. The scope of the method was tested by use of several 1,3-dioxanes and the isolated new pivalic acid derivatives were characterised.