Synthesis gas (syngas), a fundamental feedstock in chemical industry, is a mixture of hydrogen (H2) and carbon monoxide (CO).Transition metal-catalyzed hydroformylation of alkenes with syngas has been an important industrial process in the production of aldehydes and their derivatives, such as carboxylic acids, alcohols and amines (Fig.1a) [1].Large-scale consumption of syngas in industrial hydroformylations contributes to approximately 12 million tons of oxo products annually [2].However, the high pressure and harsh reaction conditions involving extremely toxic and flammable gas mixtures impede the wide application of syngas in fine chemistry, pharmaceutical industry and academic laboratories.High price facilities such as sophisticated stainless-steel reactor, gas cylinder, explosion shield, CO and H2 gas detectors, as well as the potential of toxic and inflammable gas leaking risks are important restrictions for not applying this gas in these settings.Therefore, tackling of the aforementioned shortcomings by the turning to the use of syngas surrogates can be highly attractive.Up to now, the syngas surrogates examined in a laboratory scale are mainly C1-molecules, such as formaldehyde, methanol, and formic acid.In some cases, diols, biomass-based polyols, and paraformaldehydes are applied as sources of syngas in hydroformylations (Fig.1b).