Safety in workplaces is a requirement for work sustainability. Construction workers are frequently exposed to dangerous airborne substances. While previous studies examined chemical risks in other sectors, there is limited research on occupational chemical risk perception (OCRP) among construction workers. This study focuses on evaluating OCRP in construction workers and identifying its association with socio-demographic, occupational, and training variables. In L'Aquila, Italy, a sample of male construction workers involved in post-earthquake reconstruction were enrolled in this cross-sectional study. Chemical hazard perception, occupational exposure, personal protective equipment (PPE) use, and training were all covered by our questionnaire. Although the involved 117 workers appear to be aware of dust-related risks and asbestos-related diseases, 53% think that there is no asbestos at their worksite. Respiratory protection equipment was used by 36% of the respondents. OCRP was associated with refresher training (OR = 2.56; p = 0.025); perception of noise (OR = 10.03; p = 0.027); and solar radiation (OR = 26.07; p = 0.001). Although we observed an appropriate awareness of some occupational hazards, gaps between awareness, hazard perception, and protective behavior were evident. Comprehensive site inspections and improved risk communication are necessary to assess chemical hazards and enhance work sustainability.