The spherical structure of hollow carbon spheres (HCSs) makes their contact resistance and tunnel resistance extremely sensitive to the distance between them, which can be used as a conductive filler for high-sensitivity pressure sensors. Compared with one- and two-dimensional carbon-based materials, HCSs require a higher filling concentration for constructing an effective conductive network due to their average conductivity, which affects the mechanical properties of the sensor. In a single-electron system, electrons are transferred by hopping between the nitroxyl radical monomers and when the distance between the monomers is shortened, the electron transfer rate of nitroxyl radical compounds can be increased, thus further improving their conductivity. In this work, a composite of nitroxyl radical-modified hollow carbon spheres (HCS-g-NO˙) and polydimethylsiloxane (PDMS) polymer is introduced, and the resistivity of HCS-g-NO˙ is about one magnitude lower than that of HCSs at the same filling concentration. A flexible piezoresistive sensor with HCS-g-NO˙@PDMS as the sensitive layer coated on the PET electrode is presented, in which the spacing between HCS-g-NO˙ changes, causing changes in the contact and tunnel resistances in the sensitive layer when mechanical stresses are applied. The sensor achieved a piezoresistive response of −0.55 kPa⁻¹ and the tensile response of 211 , and a sensor array of nine pixels was successfully demonstrated; thus, it can be used as a high sensitivity pressure and strain sensor.