Firefighters are at high risk to suffer potential health effects due to their chronic exposure to a countless number of air pollutants, including polycyclic aromatic hydrocarbons (PAHs) that are released during fire occurrences. Firefighters’ exposure assessment is one of the most challenging due to the logistic reasons and thus human biomonitoring represents an accurate tool to estimate total exposure. This study assesses firefighters’ total exposure to PAHs through the determination of six urinary biomarkers of exposure (OHPAHs: 1-hydroxynaphthalene, 1-hydroxyacenaphthene, 2-hydroxyfluorene, 1-hydroxyphenanthrene, 1-hydroxypyrene, and 3-hydroxybenzo(a)pyrene) and two genotoxic/oxidative-effect biomarkers (basal DNA and oxidative DNA damage). Urinary concentrations of total OHPAHs were significantly increased in subjects that were recently involved in firefighting activities, being 1-hydroxynaphthalene, 1-hydroxyacenaphthene, and 2-hydroxyfluorene the compounds with the highest increments. Concentrations of urinary 1-hydroxypyrene were below the benchmark level (0.5 µmol/mol creatinine) proposed by American Conference of Governmental Industrial Hygienists; 3-hydroxybenzo(a) pyrene, metabolite of the carcinogenic benzo(a)pyrene, was not detected. Positive correlations were found between levels of total OHPAHs and the oxidative DNA damage of exposed firefighters; data forDNA damagewas inconclusive. Evidencewas raised regarding the simultaneous use of biomarkers of exposure and of effect for the surveillance of firefighters’ health and to better estimate the potential short-term health risks. Surveillance (bio) monitoring programs are needed, principally in the most severely affected countries, to better characterize short- and long-termhealth risks. Funding: This work was financially supported by the project PCIF/SSO/0090/2019 by the Fundação para a Ciência e a Tecnologia, Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds. This work received support by UIDB/50006/2020, UIDP/50006/2020, through the project PCIF/ SSO/0017/2018 by the Fundação para a Ciência e a Tecnologia, Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds. M. Oliveira was supported by the scientific contract CEEC-Individual 2017 Program Contract CEECIND/03666/2017.