We have found a procedure for generating novel two-dimensional (2D) nanowebs in three-dimensional (3D) fibrous mats by optimization of various processing parameters during electrospinning. The electrospun fibres act as a support for the 'fishnet-like' nanowebs comprising interlinked one-dimensional (1D) nanowires. The average diameter of the nanowires contained in typical nanowebs is about one order of magnitude less than that of conventional electrospun fibres. The formation of the nanowebs of poly(acrylic acid) (PAA) and nylon-6 is considered to be due to the electrically forced fast phase separation of the charged droplets which move at high speed between the capillary tip and the collector. The formation, morphology and area density of the nanowebs in electrospun fibrous mats are strongly affected by the applied voltage, ambient relative humidity, kinds of solvents, solution concentration and distance between the capillary tip and the collector.