Among patterning technologies for organic thin-film transistors (OTFT), the fabrication of OTFT electrodes using polymer template has attracted much attention. However, deviations in electrodes alignment occur owing to a much higher coefficient of thermal expansion (CTE) of the polymer template than the CTE of the dielectric layer. Here, a novel dry blending method is described in which SiO2 nanoparticles are filled into a grooved silicon template, following by permeation of polydimethylsiloxane (PDMS) into the SiO2 nanoparticle gaps. The SiO2 nanoparticles in the groove are extracted by curing and peeling off PDMS to prepare a PDMS/SiO2 composite template with a nanoparticle content of 83.8 wt%. The composite template has a CTE of 96 ppm/°C, which a reduction of 69.23%, compared with the original PDMS template. Finally, we achieved the OTFT electrodes alignment by the composite template.