Saliva has recently been attracting attention as a patient-friendly available bio-fluid and an alternative to serum/plasma for hormone tests. LC coupled with atmospheric pressure ionization-MS/MS, especially electrospray ionization (ESI)-MS/MS, has been recently valued as a highly specific method in the analysis of salivary hormones. In this article, LC/ESI-MS/MS assays for salivary hormones are overviewed according to the papers that have been published during the last 5 years. Practical derivatization to enhance the detectabilities of hormones in ESI-MS/MS is also discussed, because a major disadvantage of using saliva is low hormone concentrations.