In this study, we explored psychometric network analysis (PNA) as an alternative method for identifying item wording effects in self-report instruments. We examined the functioning of negatively worded items in the network structures of two math-related scales from the 2019 Trends in International Mathematics and Science Study (TIMSS); Students Like Learning in Mathematics (SLLM); and Students Confident in Mathematics (SCM). We also explored how the negatively worded items functioned in network structures across demographic subgroups. Data were drawn from eight countries that represented diverse levels of math performance and cultural attitudes toward school (n = 75,972). We found that negatively worded items were distinct from the positively worded items in the SLLM and SCM item networks, and that this effect was consistent across all age- and country-level subgroups. Based on these findings, we recommend PNA as a data-driven approach for detecting wording effects effectively.