The increasing concerns regarding global warming and the scarcity of raw materials in the construction industry have led to a growing need for alternative low-carbon binders to partially replace ordinary Portland cement. To assess the suitability of pozzolans as supplementary cementitious materials (SCMs), the R3-test has been introduced and successfully validated for a wide range of materials. This test provides an opportunity to analyze the reactivity classification and study the reaction mechanisms and kinetics of novel SCMs in a well-controlled environment. In this study, the focus lies on evaluating the early reactions of lime paste samples through isothermal calorimetry tests conducted at 40 °C. However, conventional mixing methods present experimental challenges. In-situ mixing fails to achieve proper paste homogenization, while ex-situ mixing results in a temperature difference at the start of testing due to the elevated testing condition of 40 °C. To address these concerns, a novel calorimetric methodology is proposed for early detection of reactivity responses. The main concept involves establishing a baseline correction for the temperature difference caused by ex-situ mixing, which is calibrated using an inert sample. This correction allows for the extraction of the heat generated by the early reactions. Combined with the Tian time correction, this methodology enables the evaluation of early reactions in lime paste samples measured with isothermal calorimetry at 40 °C within the first 100 min after mixing. The effectiveness of this methodology was demonstrated by evaluating the early reactions and the impact of potassium sulfate on three different types of metakaolin.