The present study investigates the real-time estimation of CO2 absorption capacity (CAC) based on the electrical conductivity (EC) of low-concentration di-methyl-ethanolamine (DMEA) solutions (0.1–0.5 M). CO2 absorption experiments are conducted to measure the variation in CAC and EC during CO2 absorption, revealing a strong correlation between the two properties. The ionic conductivity of DMEAH+ formed during absorption is calculated to be 53.1 S·cm2/(mol·z), which is found to be larger than that of TEAH+ and MDEAH+. This can be attributed to the smaller molar mass and higher ionic mobility of DMEAH+. A significant finding is that the measured EC (ECM) of the DMEA solutions consistently demonstrates a lower value than the theoretically predicted value. This discrepancy is due to the larger ionic size of DMEAH+, which results in a reduction in the real mean ionic activity coefficient. This effect becomes more pronounced with increasing DMEA concentration. Consequently, a higher CAC is required to produce the same change in EC at higher amine concentrations. Based on these findings, an empirical equation is devised to estimate CAC from ECM in solutions of constant DMEA concentration. This equation will be employed as a practical approach for the in situ monitoring of CO2 absorption using DMEA aqueous solution.