Only few studies have focused on organochlorine pesticides (OCPs) in breast milk and the related health risks for women in Taiwan. Our goal is to examine breast milk OCPs and their associations with female reproductive function (infertility, gynecological diseases, and menstruation characteristics) as well as their correlation with sociodemographic parameters (age, pre-pregnant body mass index (BMI), annual incomes, population, birth year, and parity) and dietary habit. The breast milk samples were collected in southern Taiwan (n = 68) from 2013 to 2016 and the OCP residues were analyzed using high resolution gas chromatography with low resolution mass spectrometry (HRGC/LRMS). The results show that the most abundant OCP residues in the breast milk was ΣDDT with the geometric mean ± standard deviation of 9.81 ± 7.52 ng−1 lipid−1 followed by ΣHCH (0.539 ± 0.557 ng−1·lipid−1). In the principal component analysis, cis-chlordane (cis-CHL) and γ-HCH were found to be related to participants who received medical treatment for infertility, and 4,4′-DDT was associated with those who received gynecological surgery. The logistic regression showed that the odds ratio (OR) of log γ-hexachlorocyclohexane (γ-HCH) was higher for mothers who had received medical treatment for infertility than for the normal group (OR = 25.6, p = 0.035) after adjustments for age, pre-pregnant BMI, annual income, population (i.e., native-born Taiwanese), birth year, and parity. Cow milk and beef consumption as well as menstruation characteristics such as average menstrual period (>5 days), shortest menstrual period (<3 days), and women who had taken hormonal drugs were significantly associated to several OCP residues in the breast milk. In addition, ΣHCH including β-HCH and γ-HCH was correlated with annual family income and gravidity as well as cow milk and beef consumptions. Overall, γ-HCH exhibited a probable association with the infertility diseases of Taiwanese women, and dietary habit might play an important role in the female Taiwanese exposure to OCPs.