Selective transfer hydrogenation (TH) of unsaturated molecules using methanol is challenging as the in situ generated formaldehyde is prone to react with the active methylene (C-methylation) or amine (N-methylation) core of the desired product. In this work, an effective protocol is demonstrated for the selective transfer hydrogenation of CC and CO bonds in α,β-unsaturated ketones and the CN bond in imines using methanol. Under a considerably lower catalyst loading (0.1–0.5 mol%), an electron-rich bifunctional Ir-catalyst showed prominent catalytic activity towards a wide variety of substrates. Remarkably, α,β-unsaturated ketones were directly transformed into alcohols via double TH of CC and CO bonds. The TH of electron-withdrawing substrates was more favourable than that of electron-donating ones as reflected by a Hammett study. Numerous kinetic studies and DFT calculations were carried out to understand this catalytic process.