Lithium bis(oxalato) borate (LiBOB) was neutron bombarded with a flux of 2.40 × 1012 n cm−2 s−1 for 1, 2, 3 and 4 h. The neutron damaged LiBOB was studied by FT-IR and Raman spectroscopy as well as by DSC (Differential Scanning Calorimetry). It is shown that the neutron bombardment causes the radiolysis of the oxalate ligand of LiBOB producing boric acid. The kinetics of LiBOB radiolysis under neutron bombardment was fitted according to the pseudofirst order kinetics law using either the FT-IR data or the decomposition enthalpy data leading in both cases to a rate constant of 9.2 × 10−5 s−1. Pristine LiBOB is not a paramagnetic solid but after neutron bombardement it gives a very clear and stable ESR signal attributed to trapped spins in the radiolysis products.