In this work, for the first time, we reported the fabrication of polymer-derived amorphous SiCNO ceramics via electrospinning of tetraethoxysilane (TBOS), polyvinylpyrrolidone (PVP), cetrimonium bromide (CTAB), and urea combined with subsequent air calcination. The resultant products exhibited a well-defined one-dimensional (1D) hollow fiber nanostructure with mesoporous walls. The BET surface area of SiCNO hollow nanofibers is similar to 95.6m(2)/g, and the average pore diameter is sized in similar to 9nm. The movement of urea within the core of the as-spun polymeric fibers accounted for the formation of hollow nanofibers, and the thermal decomposition of polymers such as PVP, TEOS, and urea responded for the formation of mesopores within the walls. In addition, it was found that the contents of urea within the raw materials played a critically important role in the formation of SiCNO mesoporous hollow nanofibers, making their growth in a controlled manner.