Wet electrospinning is a useful method for 3-dimensional structure control of nanofibrous materials. This innovative technology uses a liquid collector instead of the metal one commonly used for standard electrospinning. The article compares the internal structural features of polycaprolactone (PCL) nanofibrous materials prepared by both technologies. We analyze the influence of different water/ethanol compositions used as a liquid collector on the morphology of the resultant polycaprolactone nanofibrous materials. Scanning electron micro-photographs have revealed a bimodal structure in the wet electrospun materials composed of micro and nanofibers uniformly distributed across the sample bulk. We have shown that the full-faced, twofold fiber distribution is due to the solvent composition and is induced and enhanced by increasing the ethanol weight ratio. Moreover, the comparison of fibrous layers morphology obtained by wet and dry spinning have revealed that beads that frequently appeared in dry spun materials are created by Plateau-Rayleigh instability of the fraction of thicker fibers. Theoretical conditions for spontaneous and complete immersion of cylindrical fibers into a liquid collector are also derived here.