This paper has developed a neuromarketing framework measuring the relationship between products and services in product–service systems (PSSs), particularly regarding its impact on PSS decision making. We divided the PSSs into different levels of product and service combinations in order to identify the impact of the various elements in PSS on decision making, particularly the key factor that induces significant variation in the purchase rate. The experiments showed the neural mechanisms behind the value perception of PSSs; this has been indicated by the appearance of N170, which is related to the cognition processing of familiarity and similarity. It is concluded that the perceived value of the product-oriented PSS is mainly determined by the product attribute, as the promotional effect of service has been clarified. The results explain the psychological and neurological activities that take place when consumers are browsing product–service bundles, which may help corporations better understand the relationships among the components in product–service bundles, providing insight for PSS innovation and service design.