<p>Adopting composite matrices has great significance for improving the performance of polymeric positive temperature coefficient (PPTC) materials. However, the uncontrollable selective distribution of fillers in different matrices induced by the differences in compatibility severely limits the flexible design and regulation of conductive networks. A solution-mixing strategy based on the solubility difference of polymer matrices in different solvents was employed to flexibly fabricate hierarchical PPTC composites, achieving the precise localization of conductive fillers. In the hierarchical structure, PVDF/TiC served as the first-level PTC material, whereas the PA1010/TiC particles acted as the other-level PTC material. The PA1010/TiC particles serving as relay stations also participated in the construction of the PVDF/TiC conductive network. Benefiting from the restriction effect of the PA1010/TiC particles for the PVDF chains and TiC fillers, the negative temperature coefficient (NTC) effect was effectively suppressed, and a maximum <i>I</i>_PTC of 8.9 was obtained. Moreover, in cyclic testing, the PVDF phase crystallized posterior to the PA1010 phase, generating compression and releasing latent heat for the PA1010 phase, which synergistically reinforced the crystallization of the PA1010 phase, enabling rapid reconstruction of long-range conductive networks in the entire system. Therefore, the reproducibility and <i>I</i>_hold of the hierarchical PPTC thermistor were significantly improved. This strategy not only breaks the bottleneck of the selective distribution of fillers in the multi-matrix of PPTC materials, but also achieves dynamic control of hierarchical conductive networks, suggesting a new pathway toward the overall improvement of the performance of PPTC thermistors.</p>