An experimental design has been developed to improve gluten-free bread formulation, on the basis of rice flour and hydroxypropylmethylcellulose (HPMC) as alternative baking ingredients. In order to improve the quality of gluten-free bread, several levels of acidic food additives (acetic acid, lactic acid, citric acid and monosodium phosphate) have been tested. The influence of these compounds on the dough and on bread properties has been determined, including a hedonic sensory test of appearance, odour, taste and texture of bread. Results suggest that monosodium phosphate yields bread producing better texture scores, associated with the highest volumes of the loaf. Discussions are made on the basis of CO2 transport pathway across the HPMC network and simultaneous interactions with acidic food additives present. Chemical properties of the acids justify the bread’s alveolus size and the preservative effects of acetic acid in the dough.