Toothache is one of the most common global health problems, and medicinal plants are widely used to relieve the associated pain and inflammation. Several studies have been conducted on the use of plants to treat toothache, but no study has comprehensively assessed the types of plants and the mechanisms of action of the phytochemical compounds involved in their analgesic effect. This review aims to bridge this gap. This is the first review to collect a large volume of data on the global use of medicinal plants used in the treatment of toothache. It presents the relevant information for dentists, researchers, and academics on using medicinal plants to treat toothache. We found that preclinical studies and state-of-the-art technology hold promise for furthering our knowledge of this important topic. In total, 21 species of medicinal plants used to treat toothache were found in America, 29 in Europe, 192 in Africa, 112 in Asia, and 10 in Oceania. The most common species were Allium sativum, Allium cepa, Acmella oleracea, Jatropha curcas, Jatropha gossypiifolia, and Syzygium aromaticum. The most commonly found family of medicinal plants was Asteraceae, followed by Solanaceae, Fabaceae, Lamiaceae, Euphorbiaceae, Rutaceae, and Myrtaceae. The most common phytochemicals found were flavonoids, terpenes, polyphenols, and alkaloids. The reported mechanisms of action involved in toothache analgesia were antioxidant effects, effects mediated by transient receptor potential channels, the γ-aminobutyric acid mechanism, and the cyclooxygenase/lipoxygenase anti-inflammatory mechanism.