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As a vital component of electronic products, the quality of the printed circuit board (PCB) assembly directly affects the applications and service life. During the reflow soldering process, the PCB assembly may suffer excessive warpage. Therefore, in order to avoid such a failure, this paper conducts the finite element simulation of the PCB assembly temperature change and the deformation process according to a theoretical model for heat transfer and then explores the causes of warpage and predicts the percentage of warpage that occurs during the reflow soldering. A reliability sensitivity analysis is creatively applied in the PCB assembly warpage study in order to uncover the quantitative influence of multiple factors with random errors on warpage. Moreover, the reliability calculation provides a theoretical basis for the allowable error range of geometric dimensions, material properties and process parameters of the PCB assembly. This research has a remarkable significance and is valuable to engineering in promoting quality and reliability, and increasing the yield of PCB assembly in mass production.