This work proposed a novel approach based on principal component analyses (PCAs) to monitor the very early-age hydration of self-compacting concrete (SCC) with varying replacement ratios of fly ash (FA) to cement at 0%, 15%, 30%, 45%, and 60%, respectively. Based on the conductance signatures obtained from electromechanical impedance (EMI) tests, the effect of the FA content on the very early-age hydration of SCCs was indicated by the predominant resonance shifts, the statistical metrics, and the contribution ratios of principal components, quantitatively. Among the three, the PCA-based approach not only provided robust indices to predict the setting times with physical implications but also captured the liquid-solid transition elongation (1.5 h) during the hydration of SCC specimens with increasing FA replacement ratios from 0% to 45%. The results demonstrated that the PCA-based approach was more accurate and robust for quantitative hydration monitoring than the conventional penetration resistance test and the other two counterpart indices based on EMI tests.