For the first time the assembly of isolated and purified MCM‐41 nanoparticles into nanofibers was realized by electrospinning. Electrospinning was conducted with a dispersion of these nanoparticles and polyvinylpyrrolidone in ethanol. The nanofibers were characterized by electron microscopy, X‐ray diffraction, elemental analysis, gas physisorption and infrared spectroscopy in diffuse reflectance. The variation of the spinning parameters was investigated in detail towards the influence on the nanofiber diameter. The change of the applied voltage and the flow rate show strong impacts on the nanofiber diameter. Therefore, the nanofiber diameter can be tailored by choosing suitable electrospinning parameters. The fiber mats with thin nanofibers were then additionally functionalized with sulfonic acid groups in a proof of principal study. The nanofiber morphology was maintained both after functionalization with thiol group and subsequent oxidation to sulfonic acid groups.