Monoalkylmercury species have been discovered in nuclear waste tanks at the Savannah River Site, a superfund nuclear waste storage site in South Carolina. Common and standard methods for organomercury speciation could not be implemented within the context of the radioanalytical facilities in Savannah River National Laboratory (SRNL) in a safe, cost-efficient manner to facilitate data-driven regulatory action. SRNL conducted development, optimization, and validation work focused primarily on combining monomethylmercury and monoethylmercury speciation into one analysis to reduce, limit analyst radiation exposure, and improve the instrumental footprint area. Sodium tetra-n-propylborate was used as a derivatizing agent to enable chromatographic resolution of monomethylmercury and monoethylmercury without serial analyses. Linear calibration of monomethylmercury and monoethylmercury ranged five orders of magnitude, producing detection limits of 0.033 pg and 7.50 pg, respectively.Calibration verifications maintained 101% and 99.1% accuracy, respectively, with mean recoveries spiked in waste sample of 98.8% and 98.4%. Dilution volume was optimized to eliminate sample distillation, reduce sample radioactivity by 100% and 99.99992% for alpha and beta/gamma radiation, improve method runtime by 337%, and decrease total instrumentation footprint by 60.4%, compared with current standard methods. This method was validated internally against certified standards and externally via interlaboratory comparison. Compared with standard methods, this work potentially represents a significant improvement in safety, efficiency, and sensitivity of industrial organomercury speciation, particularly in nuclear analysis.