Sensing materials withfifiber structures are excellentcandidates for the fabrication offlflexible pressure sensors due totheir large specifific surface area and abundant contact points. Here,an ultrathin,flflexible piezoresistive pressure sensor that consists of amultilayer nanofifiber network structure prepared via a simpleelectrospinning technique is reported. The ultrathin sensitive layeris composite nanofifiberfifilms composed of poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) and polyamide 6(PEDOT:PSS/PA6) prepared by simultaneous electrospinning.PEDOT:PSS conductivefifibers and PA6 elasticfifibers areinterwoven to form a multilayer network structure that canachieve ultrahigh sensitivity by forming a wealth of contact pointsduring loading. In particular, gold-deposited PA6fifibers as upper and lowerflflexible electrodes can effffectively increase the initialresistance. Due to this specialfifiber electrode structure, the sensor is able to generate a large electrical signal variability whensubjected to a weak external force. The devices with difffferent sensing properties can be obtained by controlling the electrospinningtime. The sensor based on the PEDOT:PSS/PA6 nanofifiber network has high sensitivity (6554.6 kPa−1at 0−1.4 kPa), fast responsetime (53 ms), and wide detection range (0−60 kPa). Signifificantly, the device maintains ultrahigh sensitivity when cyclically loadedover 10,000 cycles at 5 kPa, which makes it have great prospects for applications in human health monitoring and motionmonitoring.