Sensing materials with fiber structures are excellent candidates for the fabrication of flexible pressure sensors due to their large specific surface area and abundant contact points. Here, an ultrathin, flexible piezoresistive pressure sensor that consists of a multilayer nanofiber network structure prepared via a simple electrospinning technique is reported. The ultrathin sensitive layer is composite nanofiber films composed of poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) and polyamide 6 (PEDOT:PSS/PA6) prepared by simultaneous electrospinning. PEDOT:PSS conductive fibers and PA6 elastic fibers are interwoven to form a multilayer network structure that can achieve ultrahigh sensitivity by forming a wealth of contact points during loading. In particular, gold-deposited PA6 fibers as upper and lower flexible electrodes can effectively increase the initial resistance. Due to this special fiber electrode structure, the sensor is able to generate a large electrical signal variability when subjected to a weak external force. The devices with different sensing properties can be obtained by controlling the electrospinning time. The sensor based on the PEDOT:PSS/PA6 nanofiber network has high sensitivity (6554.6 kPa-1 at 0-1.4 kPa), fast response time (53 ms), and wide detection range (0-60 kPa). Significantly, the device maintains ultrahigh sensitivity when cyclically loaded over 10,000 cycles at 5 kPa, which makes it have great prospects for applications in human health monitoring and motion monitoring.