Aldehydes are important intermediates and products in a variety of combustion and gas-phase oxidation processes, such as in low-temperature combustion, in the atmosphere, and in interstellar media. Despite their importance, the enthalpies of formation and bond dissociation energies ( BDEs) for the aldehydes are not accurately known. We have determined enthalpies of formation for acetaldehyde, propanal, and butanal from thermodynamic cycles, using experimentally measured reaction and formation enthalpies. All enthalpy values used for reference molecules and reactions were first verified to be accurate to within around 1 kcal mol(-1) using high-level ab initio calculations. Enthalpies of formation were found to be -39.72 +/- 0.16 kcal mol(-1) for acetaldehyde, -45.18 +/- 1.1 kcal mol(-1) for propanal, and -49.27 +/- 0.16 kcal mol(-1) for butanal. Enthalpies of formation for these three aldehydes, as well as for pentanal, hexanal, and heptanal, were calculated using the G3, G3B3, and CBS-APNO theoretical methods, in conjunction with bond-isodesmic work reactions. On the basis of the results of our thermodynamic cycles, theoretical calculations using isodesmic work reactions, and existing experimental measurements, we suggest that the best available formation enthalpies for the aldehydes acetaldehyde, propanal, butanal, pentanal, hexanal, and heptanal are -39.72, -45.18, - 50.0, -54.61, -59.37, and -64.2 kcal mol(-1), respectively. Our calculations also identify that the literature enthalpy of formation of crotonaldehyde is in error by as much as 1 kcal mol(-1), and we suggest a value of -25.1 kcal mol(-1), which we calculate using isodesmic work reactions. Bond energies for each of the bonds in the aldehydes up to pentanal were calculated at the CBS-APNO level. Analysis of the BDEs reveals the RsCH(2)CH=O bond to be the weakest bond in all aldehydes larger than acetaldehyde, due to formation of the resonantly stabilized vinoxy radical ( vinyloxy radical/formyl methyl radical). It is proposed that the vinoxy radical as well as the more commonly considered formyl and acetyl radicals are important products of aldehyde combustion and oxidation, and the reaction pathways of the vinoxy, formyl, and acetyl radicals are discussed. Group additivity values for the carbon-oxygen-hydrogen groups common to the aldehydes are also determined. Internal rotor profiles and electrostatic potential surfaces are used to study the dipole induced dipole-dipole interaction in the synperiplanar conformation of propanal. It is proposed that the loss of this dipole-dipole interaction in (RCHCH2CH)-H-.=O radicals causes a ca. 1-2 kcal mol(-1) decrease in the aldehyde C-H and C-C bond energies corresponding to (RCHCH2CH)-H-.=O radical formation.