Organic peroxides (ROOR′), solid or liquid with the bivalent OO structure. Relatively unstable and highly reactive molecules due to the presence of an oxygen–oxygen linkage. The oxygen–oxygen bond may be cleaved to form highly reactive free radicals and react with many substances (e.g., metals, acids, and bases). ROORs are used in plastics, rubbers, and many industries as initiators, accelerators, promoters, catalysts, activators, and more. Major concerns with ROORs are associated with fires, explosions, and corrosiveness. Reactive oxygen species and free radicals may lead to DNA damage and mutagenesis. Recent work from government agents, academic research laboratories, and manufacturing organizations have focused on physical hazards classification and categorization; and producing best practice protocols for safe handling and storage, control of temperatures, self‐accelerating decomposition temperatures, spills cleaning, disposal, and treatment of ROORs residues. These efforts allow compliance with countries and international regulations. Potential health hazards are associated with eye and skin contact, inhalation, and ingestion. Acute exposure may lead to irritation, allergic response, and potential damage to the eye and skin. As with any irritant or corrosive, dose is a critical consideration with respect to understanding the risk. Chronic exposures, mostly understood in animals but there are human data, can cause a myriad of effects. These may range from respiratory illnesses, to liver, kidney damage, and cancer. The manufacturer's SDS of individual chemical may provide toxicity information. This chapter summarizes chemical‐specific toxicity information on 77 organic peroxide compounds grouped in eight physical hazard categories. NIOSH has fully validated the method for benzoyl peroxide. NTP has released a report on the toxic effects of
t
‐butyl perbenzoate and it deserves to be considered. Exposure assessment methods when available were presented. Future research needs to focus on epidemiological and toxicological studies of ROORs.