Although exposure to antibiotics at a critical developmental time window has been implicated in mental health in observational and experimental studies, very limited bio-monitoring data are available for exposure to antibiotics associated with child mental disorders. The goal of our study was to examine the association between urinary exposure of children to antibiotics and mental health. The participants were 278 children from 256 eligible families in the urban–rural fringe of Fuyang city in China since June in 2017. A single-point urine sample was collected to measure the antibiotic concentrations to characterize the exposure levels. A total of 45 antibiotics from nine classes and their two metabolites were monitored through liquid chromatography electrospray tandem mass spectrometry. We used multivariable regressions to estimate the covariate-adjusted associations between urine–antibiotic concentrations and mental impairments, as assessed using the parent version of Strengths and Difficulties Questionnaire. Among the participants, ciprofloxacin was associated with an increased risk of mental disorders at both lower concentrations (OR = 4.06; 95% CI 1.69–9.78) and higher concentrations OR = 6.04; 95% CI 2.59–14.08). After categorizing the detected antibiotics, the positive associations were observed between abnormal score in total difficulties and higher levels exposure to fluoroquinolones (OR = 2.83, 95% CI 1.38–5.80) and antibiotics preferred for veterinary use (PVAs) (OR = 3.20; 95% CI 1.41–7.27), respectively. Our findings suggest that ciprofloxacin, fluoroquinolones and PVAs, probably from contaminated food or environment, may be associated with child mental disorders.