Graphite morphology has a significant influence on mechanical properties such as tensile strength and hardness in nodular cast iron (NCI). Compared to the detection of graphite nodularity, there is relatively less ultrasonic simulation and detection experiment research on the graphite size. Therefore, it is of great importance to study rapid nondestructive testing methods for the internal graphite size of NCI. This study establishes a simulation model of nonlinear ultrasonic penetration longitudinal wave detection for graphite size. The acoustic nonlinearity parameter (ANP) is used to characterize the graphite size. Nonlinear ultrasonic detection experiments on the internal graphite size are conducted to verify the reliability of the nonlinear ultrasonic simulation model. The simulation and experimental results show that the ANP of penetrating longitudinal waves decreases with the increase of average graphite diameter. The relationship between ANP and internal graphite size is established. Moreover, the experimental results verified the accuracy of the numerical model. The decrease in ANP may be related to the decrease in the number of grain boundaries. Therefore, the nonlinear ultrasonic technique is an effective method for characterizing the internal graphite size. The establishment of a nonlinear ultrasonic simulation model for graphite size in NCI lays the research foundation for nonlinear ultrasonic microstructure characterization experiments.