The process modeling for the growth rate of pulsed laser deposition (PLD)-grown ZnO thin films was investigated using neural networks (NNets) based on the back-propagation (BP) algorithm and PCA-based NNets using photoluminescence (PL) data. D-optimal experimental design was performed and the growth rate was characterized by NNets. PCA-based NNets were then carried out in order to build the model by PL data. The statistical analysis for those results was then used to verify the fitness of the nonlinear process model. Based on the results, this modeling methodology can explain the characteristics of the thin film growth mechanism varying with process conditions and the model can be analyzed and predicted by the multivariate data.