Emissions of formaldehyde and volatile organic compounds (VOCs) from building materials may result in poor indoor air quality. The emission process can be divided into three stages over time: early, transition, and equilibrium stages. In existing studies, mass transfer models without distinguishing the early and transition stages have been widely used for characterizing the formaldehyde/VOC emissions, with three key parameters involved in these models. Many methods have been proposed for determining these parameters by fitting the corresponding models to experimental data. However, multiple groups of best-fit parameters might coexist if experimental data are obtained at the early stage (to shorten the experimental time). Therefore, we developed a novel mass transfer model to describe the early-stage emissions by assuming the building material as semi-infinite medium. The novel model indicated that the early-stage emission was governed by only two parameters, instead of three parameters, which explained the reason for the multi-solution problem of existing methods. Subsequently, the application condition of the early-stage model was clarified, showing that the early stage was very common in the emissions of formaldehyde/VOCs. Finally, a novel approach for characterizing the emissions of formaldehyde/VOCs from building materials was proposed to eliminate the negative effects of the multi-solution problem.