Purpose: This study analyzed the association between sex hormone concentrations and stage/condition in patients with prostate cancer. Materials and methods: The concentrations of sex hormones, including testosterone (total, free, and bioavailable), sex hormone-binding globulin (SHBG), luteinizing hormone (LH), and follicle-stimulating hormone (FSH), were measured in 415 patients diagnosed with prostate cancer. Differences in serum hormone concentrations after receiving androgen deprivation therapy (ADT) and after withdrawal from ADT were evaluated. Pathologic characteristics were assessed in the 225 patients unexposed to ADT with a history of radical prostatectomy. Logistic regression analysis was performed to identify factors predictive of unfavorable pathology (Grade ≥3, ≥T3a, or N1). Results: Of the 415 prostate cancer patients, 130 (31.3%) were assessed before treatment, 171 (41.2%) after surgery, 35 (8.4%) after biochemical recurrence, and 59 (14.2%) during ADT, whereas 20 (4.8%) had castration-resistant prostate cancer. FSH was significantly lower after compared to before prostatectomy (3.229 ± 4.486 vs. 5.941 ± 7.044 mIU/mL, p < 0.001). LH, FSH, and testosterone decreased significantly 3 months after starting ADT, but increased 3 months after ADT withdrawal, whereas SHBG was unchanged. Multivariate analysis showed that high LH (odds ratio [OR]: 1.59, 95% confidence interval [CI]: 1.03–2.47, p = 0.0376) and prostate-specific antigen (PSA) (OR: 1.13, 95% CI: 1.03–1.24, p = 0.0133) concentrations were significantly associated with a high risk of unfavorable pathology. Conclusions: Sex hormones, including LH, FSH, and testosterone, were affected by ADT. The FSH level decreased after radical prostatectomy. High baseline LH concentration in patients unexposed to ADT was associated with an unfavorable pathology.