The relationships of cooling rate with microstructure and thermal conductivity of vermicular graphite cast iron (VGI) cylinder block were studied, which are important for design and optimization of the casting process of VGI cylinder blocks. Cooling rates at different positions in the cylinder block were calculated based on the cooling curves recorded with a solidification simulation software. The metallographic structure and thermal conductivity were observed and measured using optical microscopy (OM), scanning electrical microscopy (SEM) and laser flash diffusivity apparatus, respectively. The effects of the cooling rate on the vermicularity, total and average areas of all graphite particles, and the pearlite fraction in the VGI cylinder block were investigated. It is found that the vermicularity changes in parabola trend with the increase of cooling rate. The total area of graphite particles and the cooling rate at eutectoid stage can be used to predict pearlite fraction well. Moreover, it is found that the thermal conductivity at room temperature is determined by the average area of graphite particles and pearlite fraction when the range of vermicularity is from 80% to 93%. Finally, the quantitative models are established to calculate the vermicularity, pearlite fraction, and thermal conductivity of the VGI cylinder block.