This paper evaluates the complexities of radiocarbon (14C) dates from soil organic matter (SOM) in archaeological scenarios. The aqueous NaOH-insoluble residual SOM from Neolithic to medieval sites in NW Spain produced consistently older calibrated 14C ages than NaOH-extractable SOM. Using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS), we analyzed the molecular composition of these SOM fractions, aiming to understand the differences in 14C ages and to gain insight on SOM dynamics in relation to age fractionation. The molecular composition of the NaOH-extractable SOM, which accounts for roughly two-thirds of total SOM, has a larger proportion of microbial detritus than the NaOH-insoluble SOM. This might suggest that the discrepancies between the two fractions is due to microbial rejuvenation in the extractable fraction, leading to 14C results that are younger than the activity that is to be dated. However, archaeological evidence presented here unambiguously shows that the 14C age of the extractable SOM provides the more accurate age for the targeted activity, and that the insoluble fraction contains inherited old carbon. After statistical data evaluation using Partial Least Squares-Regression (PLS-R), it is concluded that this inherited SOM is a mixture of Black Carbon from wild and/or domestic fires and recalcitrant aliphatic SOM. Cruz Ferro-Vázquez has been funded by the People Programme (Marie Curie Actions) of the European Union’s Horizon 2020 Programme (tRRACES-H2020-MSCA-IF-2014-657355). Radiocarbon analyses have been funded by the Institute of Heritage Sciences from the Spanish National Research Council (Incipit-CSIC) and the Consolider Programme CSD2007-0058 (MINECO, Spain).