Humic acid substances (HAs) in natural soil and sediment environments affect the retention and degradation of insensitive munition compounds and legacy high explosives (MCs): 2,4-dinitroanisole (DNAN), DNi-NH4+, N-methyl-p-nitroaniline (nMNA), 1-nitroguanidine (NQ), 3-nitro-1,2,4-triazol-5-one (NTO; neutral and anionic forms), 2,4,6-trinitrotoluene (TNT), and 1,3,5-trinitro-1,3,5-triazinane (RDX). A humic acid model compound has been considered using molecular dynamics, thermodynamic integration, and density functional theory to characterize the munition binding ability, ionization potential, and electron affinity compared to that in the water solution. Humic acids bind most compounds and act as both a sink and source for electrons. Ionization potentials suggest that HAs are more susceptible to oxidation than the MCs studied. The electron affinity of HAs is very conformation-dependent and spans the same range as the munition compounds. When HAs and MCs are complexed, the HAs tend to radicalize first, thus buffering MCs against reductive as well as oxidative attacks.