This study evaluates for the first time organophosphorus flame retardant (OPFR) occurrence in the Alboran Sea delphinids (Spain). OPFRs were detected in all the individuals with concentration levels up to 24.7 μg/g lw. Twelve out of sixteen tested analytes were detected, being TBOEP which presented the highest detection frequency, and IDPP which presented the highest levels of concentration. OPFR distribution in different tissues (blubber, brain, kidney, muscle and liver) was evaluated. The pattern distribution showed the highest contribution for blubber (mean value of 68%) and the lowest contribution for liver (mean value of 2%). Seven OPFRs were detected in brain samples showing their capacity to surpass the blood-brain barrier and reach the brain. Moreover, high affinity for the brain tissue was observed. This is extremely important due to the neurotoxic effects of several compounds such as TCEP and TNBP. OPFR levels were compared with previously published PBDE concentrations, and no significant differences were observed. Taking into account the lower use and lower bioaccumulation and biomagnification capacities of OPFRs, this could indicate an additional OPFR source of pollution in addition to their use as FRs.