A novel approach, i.e. manipulating the size of incorporated polymer matrix particles, was proposed to tune the positive temperature coefficient (PTC) characteristics of carbon nanotubes (CNTs)/polypropylene (PP) composites with a segregated microstructure. For the conductive properties of CNTs/PP composites, the percolation threshold decreased from 1.32vol% to 0.44vol% when the matrix particle size enlarged from 20 to 1200µm, showing an inverse correlation effect. The controllable PTC characteristics in resistivity are attributed to the microstructure development of conductive pathways and the heat-induced volume expansion of polymer matrix particles. An extremely high PTC material has also been achieved through this method. The present work provides an effective route to acquire a tunable temperature-resistivity sensor.