The formation of typical low-temperature oxidation products is observed in laminar premixed low-pressure flames investigated by photoionization molecular-beam mass spectrometry at the Swiss Light Source. The C₁-C₄ alkyl hydroperoxides can be identified in n-butane- and 2-butene-doped hydrogen flames by their photoionization efficiency spectra at m/z 48, 62, 76, and 90. C₁-C₃ alkyl hydroperoxides are also observed in a propane-doped hydrogen flame and in a neat propane flame. In addition, threshold photoelectron spectra reveal the presence of the alkyl hydroperoxides. In the 2-butene/H₂ flame, the photoionization spectrum at m/z 88 also enables the identification of butenyl hydroperoxides by comparison with calculated ionization energies of the alkenyl hydroperoxides and a literature spectrum. The low-temperature species are formed close to the burner surface with maximum mole fractions at 0.25-0.75 mm above the burner. At 0.5 mm, even the methylperoxy radical (CH₃OO) is measured for the first time in a laminar premixed flame. The rate of production analyses show that consumption of the hydroperoxyalkyl radicals results in the formation of cyclic ethers. In the n-butane/H₂ flame, ethylene oxide, oxetane, and methyloxirane are identified. Besides expected small oxygenated species, for example, formaldehyde or acetaldehyde, the larger C₄ oxygenates butanone (C₂H₅COCH₃) and 2,3-butanedione (C₄H₆O₂) are formed in the two C₄ hydrocarbon-doped hydrogen flames. Quantification of alkyl hydroperoxides with estimated photoionization cross sections based on the corresponding alcohols, which have similar photoelectron structures to the alkyl hydroperoxides, shows that mole fractions are on the order of 10^-5-10^-6 in the n-butane/H₂ flame. Measurements are corroborated by simulations, which also predict the presence of some peroxides in detectable concentrations, that is, mole fractions larger than 10^-7, under the investigated conditions. The observation of peroxide species and cyclic ethers in the investigated laminar premixed flames give new insights into the contribution of low-temperature combustion chemistry in a flame.