Polyoxometalate H5PMo10V2O40/SiO2 (HPMoV/SiO2) nanofibers with a mesoporous structure were fabricated through combined electrospinning and surfactant-directing pore formation technique. These heterogeneous nanofibers were characterized by a wide variety of techniques to show mesoporous structure, high surface area, excellent stability, nanofiber morphology, highly efficient activity and selectivity towards the oxidation of starch and 5-hydroxymethylfurfural (5-HMF) either by H2O2 or by oxygen. POM/SiO2 nanofibers were suitable for oxidation of starch by H2O2 and oxidation of 5-HMF by O-2 with high efficiency of 0.58 mol per 100 g carboxyl content and 89.2% yield of DFF; these results are comparable with those obtained using homogeneous H5PMo10V2O40 and HPMoV/SiO2 without nanofiber morphology. Furthermore, HPMoV/SiO2 nanofibers could be easily recycled and reused at least ten times with no significant loss of catalytic activity due to their nanofiber morphology.