The objectives of the study were to examine occupational exposure to phthalates of hairdressing apprentices from Slovakia (n = 74, 89.2% females; 10.8% males), outcomes related to body composition and pulmonary functions. We used high-performance liquid chromatography and tandem mass spectrometry to the quantified urinary concentration of phthalates. Pulmonary function test (PFT), anthropometric measurements, and questionnaire were also conducted. We observed a decrease of % of predicted values of forced vital capacity (FVC% of PV) related exposure to mono(2-ethyl-5-oxohexyl) phthalate (MEOHP; p = 0.054) and sum of bis(2-ethylhexyl) phthalate metabolites (∑DEHP; p = 0.037), and a decrease of % of predicted values of vital capacity (VC% of PV) related to exposure to MEOHP, ∑DEHP (p = 0.008), and mono(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP; p = 0.014) in females. We detected associations between forced vital capacity (FVC) with weight (p = 0.002) and fat-free mass index (FFMI, p = 0.010). Vital capacity (VC) and VC% of PV increased with weight, body mass index (BMI), waist circumference (WC), hip circumference (HC), waist-hip ratio (WHR), the waist-height ratio (WHtR), fat mass index (FMI) and FFMI in females (p ≤ 0.014). Results of multivariate regression between PFT and anthropometric parameters adjusted to phthalates indicated exposure to MnBP and MEHP, changing body structure (BMI and FMI), subsequently affecting values of FEV1/FVC.