The current study illustrates how an empirical psychological network approach can be employed to shed light onto the interplay of risk perception and related psychological variables. In doing so, we present a case study on laypeople’s perception of risk related to the handling of hazardous substances in their direct living environment, which combines different levels of the integrative risk perception framework in a network estimated with survey data from Dutch inhabitants (N = 1,026). Additionally, we examine the impact of a form of personal relevance by comparing cities (i.e., Zaandam nearby a chemical cluster [n = 457] and Deventer with less chemical companies [n = 569]). Results showed how, in the context of handling hazardous substances, 1) the different levels of the integrative risk perception framework are interrelated, 2) this approach can help prioritize levels of the framework and specific elements for future research (i.e., cognitive-affective factors appear to be relatively important), and 3) comparing the risk perception networks of different cities revealed that they are generally comparable, although differences in relations between specific variables can be observed. Future research should obtain insight into directions of relations between variables in the risk perception network related to handling hazardous substances to improve our understanding of the network dynamics. Employing a psychological network approach in other risk contexts could improve the understanding of risk perception in more safety domains.