Photoactivation of tetrazoles to form nitrile imines primed for 1,3-dipolar cycloaddition reactions is of widespread utility in chemistry. In contrast, the corresponding thermal reactions usually possess prohibitively high barriers and have garnered significantly less attention. Here, computational chemistry at the M06-2X/6-31+G(d,p) level of theory with SMD solvent corrections is used to show that these thermal activation barriers can be significantly reduced through the use of nonconjugated charged functional groups (CFGs). For 2,5-dimethyl-tetrazole, a positive CFG on the N-methyl (2-position) lowers the fragmentation barrier by around 80 kJ mol-1 in the gas phase, while a negative charge has a smaller opposite effect. These CFG effects remain significant even in polar solvents, with barrier lowering on the order of 30 kJ mol-1 in dimethyl sulfoxide and acetonitrile. In practical terms, the positive CFG decreases the fragmentation half-life of 2,5-dimethyl-tetrazole in refluxing o-xylene from 300,000 years to 1 week. While the resulting nitrile imine is stabilized, its subsequent 1,3-cycloaddition with N-methylmaleimide remains highly facile. Electrostatic effects on a range of 2-phenyl-5-methyltetrazoles, 2-methyl-5-phenyl-tetrazoles, and 2,5-diphenyl-tetrazoles follow similar trends and are explicable largely in terms of the stabilization of the developing dipole in the transition state.