The di(hydroperoxy)adamantane adducts of water (1) and phosphine oxides p-Tol3PO·(HOO)2C(C9H14) (2), o-Tol3PO·(HOO)2C(C9H14) (3), and Cy3PO·(HOO)2C(C9H14) (4), as well as a CH2Cl2 adduct of a phosphole oxide dimer (8), have been created and investigated by multinuclear NMR spectroscopy, and by Raman and IR spectroscopy. The single crystal X-ray structures for 1-4 and 8 are reported. The IR and 31P NMR data are in accordance with strong hydrogen bonding of the di(hydroperoxy)adamantane adducts. The Raman ν(O-O) stretching bands of 1-4 prove that the peroxo groups are present in the solids. Selected di(hydroperoxy)alkane adducts, in combination with AlCl3 as catalyst, have been applied for the direct oxidative esterification of n-nonyl aldehyde, benzaldehyde, p-methylbenzaldehyde, p-bromobenzaldehyde, and o-hydroxybenzaldehyde to the corresponding methyl esters. The esterification takes place in an inert atmosphere, under anhydrous and oxygen-free conditions, within a time frame of 45 minutes to 5 hours at room temperature. Hereby, two oxygen atoms per adduct assembly are active with respect to the quantitative transformation of the aldehyde into the ester.