This paper describes the results of tests on the influence of human saliva and its substitutes on tribological characteristics of friction pairs. Each pair consists of enamel and one of the following materials: ceramics, the Meridian B2 dental composite, the GK dental amalgam, and Ti-6Al-4V titanium alloy. The saliva substitutes used were prepared using pyrophosphates, xanthan gum, and mucins dissolved in a saline buffer. The results of the tribological tests show that the values of the parameters under investigation (coefficient of friction and linear wear) were different from each other. Some similarity was observed between the evaluated level of wear characteristics after the friction process in the environment of human saliva and that in the environment of one of the mucins tested. Microscopic observations of the surfaces of the enamel samples after friction revealed varied forms of tribological wear.