Oral care compositions containing agents that are effective for treating and modifying teeth and mucosal surfaces to be hydrophobic are disclosed. Hydrophobic modification of teeth and other oral cavity surfaces imparts a variety of end use benefits including prevention of caries, erosion, wear, staining, sensitivity and desquamation as well as providing shine, smoothness and positive tooth feel benefits. The compositions contain selected surface active organophosphate compounds that deposit and adhere to teeth and other oral cavity surfaces forming a hydrophobic coating having prolonged retention thereon. By forming a &ldquohydrophobic coating&rdquo on the oral cavity surface is meant that the hydrophobic character of the surface is increased as measured, for example, by an increase of at least about 10 degrees in the water contact angle of the surface after treatment. The increased hydrophobic character of the surface is maintained for a period of at least about 5 minutes and desirably longer such as at least about 10, at least about 20 or at least about 30 minutes. The compositions may contain additional hydrophobic materials to further increase hydrophobicity of the surface and/or functionality of the coating to provide surface protection and many other benefits.