In this paper, we report a facile method of fabricating size-controlled three-dimensional (3D) polycaprolactone (PCL) micro/nanofiber structure using a modified electrospinning supplemented with a specially designed solvent bath in which the flow rate of the solvent (EtOH) was controlled. By varying the flow rate of the EtOH into the grounded bath and the electrospinning parameters including a distance between the nozzle and target, the height, diameter, porosity, and micro/nanofiber size of the 3D structures were controlled. To show stable micro/nanofibrous structures under the fabricating conditions, we characterized a process diagram for various flow rates of EtOH and weight percents of PCL. We believe that this modified electrospinning process may be a new means of fabricating micro/nanofibrous 3D structures.