The products from the alkylation of silver hyponitrite with tert-butyl bromide, tert-amyl bromide, p-tert-butyl benzylbromide, and chlorotriethylsilane have been determined. In the reaction of tert-butyl bromide the formation of three new products, namely, (Z)-N-tert-butyl-N'-tert-butoxydiazene-N-oxide {(CH3)(3)CN(O)NOC(CH3)(3)}, 1D, trans-mono-O-tert-butylhyponitrous acid {(CH3)(3)CONNOH}, 2A, and (Z)-N-tert-butyl-N'-hydroxydiazene-N-oxide {(CH3)(3)CN(O)NNQH}, 2D, is observed together with the formation of the known trans-di-O-tert-butyl hyponitrite {(CH3)(3)CONNOC(CH3)(3)}, 1A. The reaction with tert-amyl bromide also yielded the corresponding tert-amyl derivatives. However, from the reactions of p-tert-butylbenzyl bromide and chlorotriethylsilane with silver hyponitrite, the corresponding trans-di-O-tert-alkylhyponitrites were obtained as the only alkylated products. The differential reactivity of the two sets of halides with silver hyponitrite is explained in terms of the higher stability of the cations generated from the former halides in comparison to those generated from the latter halides. The thermal decomposition data and UV-visible spectroscopic data are reported for all of the products. Crystallographic structural data are reported for two of the products, namely, Q-N-tert-butyl-K-tert-butoxydiazene-N-ox, 1D, as its hyponitrous acid adduct, (CH3)(3)CN(O)NOC(CH3)(3). 1/2HONNOH, and trans-di-O-p-tert-butylbenzyl hyponitrite, {p(CH3)(3)C}C6H4CH2ONNOCH2C6H4-p-{C(CH3)(3)}. Theoretical calculations using ab initio density functional theory (B3LYP) are reported for the hyponitrite dianion, trans-mono-O-methylhyponitrite anion, (Z)-N-methyl-N'-hydroxylatodiazene-N-oxid anion, and for the methylation transition states. On the basis of the products isolated from the reactions of tert-butyl bromide and tert-amyl bromide and the theoretical calculations, a pathway is proposed to account for the observed product distributions where O/O-dialkylation is found in the trans(E) products and O/N-dialkylation is found in the cis(Z) products.