Disclosed are oral care compositions comprising selected surface-active organophosphate compounds and methods of use to provide protection of teeth from erosion caused by the action of chemicals, such as harsh abrasives and acids. The surface-active organophosphate compounds are substantive to teeth, the phosphate groups binding the calcium in teeth and thus preventing loss of calcium from dissolution when contacted with acids. The organophosphate compound may also deposit a protective surface coating that prevents contact of teeth with erosive challenges. Selected organophosphate compounds contain one or more phosphate groups and are combined in the oral care composition with one or more of a fluoride ion agent, an antimicrobial agent preferably selected from quaternary ammonium compounds and polyvalent metal salts, an anticalculus agent and additional surfactant, to provide benefits including superior anti-erosion, anticaries, antiplaque and anti-staining as demonstrated by enhanced fluoride uptake, remineralization, resistance to acid demineralization and antimicrobial activities, resulting in improved overall tooth health, structural integrity and appearance.