Background & Objective: The rapid growth of the technological use of nanomaterials (NMs) has led to a consequent increase in their aero dispersion. This exposure may represent a risky condition for a large number of workers. The study aimed to assess the relationship between the chronic exposition of workers exposed to NMs and the biological response, quantified using some internal-dose and early biological effect biomarkers measured in a non-invasive way. Methods: 59 subjects were recruited as exposed to NMs, 26 working with “EPC” paints and coatings, and 33 with “ECC” construction chemicals. 41 unexposed subjects were enrolled as controls. At the end of the working shift, each subject provided a spot of urine, for metal quantification by ICP-MS, and an Exhaled Breath Condensate (EBC) sample, to quantify nanoparticles and local inflammation by Nanoparticles Tracking Analysis (NTA) and ELISA technique, respectively. Differences between groups and companies were tested by Kruskal-Wallis tests, according to the data distribution. Results: workers exposed to EPC and ECC demonstrated significantly higher nanoparticles concentration in EBC (p<0.0001) when compared with unexposed. Regarding inflammation, high sensitivity-CRP, interleukin (IL)-1β, and TNF-α showed significantly higher levels (p<0.0001) in EPC and ECC, when compared to unexposed. Conversely, IL-10 was significantly higher only in ECC compared to unexposed (p<0.001). Metals in urine revealed the same trend for 29Si, 47Ti, and 118Sn, with higher significant levels in both EPC and ECC when compared to unexposed (p<0.0001, p<0.0001, and p=0.001, respectively). 52Cr and 27Al proved no differences between workers from different companies. Conclusions: The results support a possible relationship between nanoparticle exposure and particle load in the airways, which in turn may cause both sustained inflammation and higher levels of metal in urine. Further investigations on these biomarkers in other occupational scenarios could be useful to devise new preventive strategies.