Successful sucrose replacement in cake recipes requires thorough understanding of its functionalities and those of potential substitutes during cake production. We show that effective sucrose substitutes provide sufficient aqueous cake batter phase (i.e. batter liquor) with low proton mobility (assessed with time-domain 1H NMR relaxometry) and high viscosity, and ensure sufficient air incorporation during batter mixing, along with appropriate timings of starch and protein transitions during baking. Maltitol and oligofructose are very soluble and, like sucrose, provide adequate batter liquor quantities with low water mobility and high viscosity, while poorly soluble mannitol does not. However, differential scanning calorimetry and rapid viscosity analyses show that oligofructose fails to provide appropriate timings of starch gelatinisation and protein denaturation, leading to poor cake texture. That the shortcomings of mannitol (in terms of solubility) and oligofructose (in terms of biopolymer transitions) can be overcome by using mixtures thereof is relevant for the baking industry.