Organophosphate triesters (PEFRs) are used increasingly as flame retardants and plasticizers in a variety of applications, such as building materials, textiles, and electric and electronic equipment. They have been proposed as alternatives to brominated flame retardants. This updated review shows that biomonitoring has gained incrementally greater importance in evaluating human exposure to PEFRs, and it holds the advantage of taking into account the multiple potential sources and various intake pathways of PEFRs. Simultaneous and extensive internal exposure to a broad range of PEFRs have been reported worldwide. Their metabolites, mainly dialkyl or diaryl diesters, have been used as biomarkers of exposure and have been ubiquitously detected in the urine of adults and children in the general population. Concentrations and profiles of PEFR urinary metabolites are seen to be variable and are highly dependent on individual and environmental factors, including age, country regulation of flame retardants, and types and quantities of emissions in microenvironments, as well as analytical procedures. Additional large biomonitoring studies, using a broad range of urinary diesters and hydroxylated metabolites, would be useful to improve the validity of the biomarkers and to refine assessments of human exposure to PEFRs.