Radiation induced damage of extractant molecules is a well-known phenomenon responsible for reducing efficiency and increasing the waste and cost of reprocessing used nuclear fuel (UNF). As such, understanding early-stage (pico- to nanoseconds) radiation-induced reaction mechanisms is essential for informing the design of next generation extractants with enhanced radiation robustness. Here we utilized picosecond and nanosecond electron pulse radiolysis experiments to probe the early-stage radioactive environment experienced by the organic phase extractant N,N,N',N'-tetraoctyldiglycolamide (TODGA), proposed for separating highly radioactive trivalent minor actinides (specifically americium and curium) from the trivalent lanthanides. Using comparisons to the similar ionization potential (IP) solute p-xylene, this work determined the mechanism of reaction with the ionized diluent (i.e., n-dodecane radical cation, DD˙+) is hole transfer to produce TODGA˙+. At high TODGA concentrations (>100 mM), the majority of this transfer occurs faster than 10 ps via the capture of DD˙+ holes prior to their solvation with a C37 = 300 mM. The surviving solvated holes were captured with k = (2.38 ± 0.15) × 1010 M-1 s-1. Attempts at subsequent hole transfer to lower IP solutes found that only 10% of holes were transferred, indicating bond rupture of TODGA˙+ occurs within 2.6 ns at 200 mM TODGA. Possible reaction pathways for the rapid decomposition of TODGA˙+ were explored using a combination of experiments and density functional theory (DFT) calculations.