Objective This study was performed to investigate the effects of age and sex on 10 salivary steroid hormones and analyze the correlations between salivary and plasma hormones. Methods The concentrations of 10 salivary steroid hormones in 1090 Chinese adult volunteers were examined using liquid chromatography–tandem mass spectrometry, and a related investigation was performed on the concentrations of salivary hormones in this population. Results The concentrations of androstenedione (A4), 17α-hydroxyprogesterone (17-OHP), aldosterone (ALD), cortisone (COR), corticosterone (CORT), cortisol (F), progesterone (P), and testosterone were significantly different between men and women (Student’s t-test). Differences in 17-OHP and ALD concentrations were highly significant between women in the follicular and luteal phases of their menstrual cycle (Student’s t-test). Five salivary steroid hormones (17-OHP, A4, CORT, COR, and F) significantly decreased with increasing age (Kruskal–Wallis test). A high linear correlation between salivary and plasma 17-OHP, P, A4, and F were observed with obvious sex-related differences (Pearson’s correlation, r > 0.7). Conclusions Our results provide important knowledge regarding the descriptive characteristics of salivary hormones in relation to age and sex and their correlations with plasma hormones.