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We studied occupational exposure to phthalates from first-morning-void urine sample of hairdressing apprentices by HPLC-MS/MS analyses and association with health status. Metabolites of mono(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP), mono ethyl phthalate (MEP), mono-n-butyl phthalate (MnBP) and mono-iso-butyl phthalate (MiBP) were detected in all urine samples, followed by metabolites mono(2-ethyl-5-oxohexyl) phthalate (MEOHP) and mono(2-etylhexyl) phthalate (MEHP) occurring in 97.06% and 86.76% of samples, respectively. Positive associations for females were observed between MnBP and fat-free mass index (FFMI) and age; negative associations were found between MEHP, MEOHP, MEHHP, sum of MEHP, MEHHP, MEOHP and vital capacity and also between MEHP and forced vital capacity (FVC of predicted value (PV)). Lengths of exposure were associated to MnBP, MEHHP, and MEP. We also documented positive associations between anthropometry (body mass index, waist-to-height ratio (WHtR), FFMI, fat mass index) and pulmonary function FVC% of PV for females and negative associations between WHtR, waist-to-hip ratio, FFMI and ratio of forced expiratory volume in 1 s (FEV1) to FVC (FEV1/FVC). We assume that factors of occupational environment of hairdressing apprentices are affected by phthalates and resulted in negative outcomes in breathing mechanism and influence of body composition. Adipose tissue could play role as confounding factor in urine excretion of phthalates because of their lipid solubility and accumulation.