Compound-specific radiocarbon analysis (CSRA) of benzene polycarboxylic acids (BPCAs) yields molecular-level, source-specific information necessary to constrain isotopic signatures of pyrogenic carbon. However, the purification of individual BPCAs requires a multistep procedure that typically results in only microgram quantities of the target analyte(s). Such small samples are highly susceptible to contamination by extraneous carbon, which needs to be minimized and carefully accounted for in order to yield accurate results. Here, we undertook comprehensive characterization and quantification of contamination associated with molecular radiocarbon (14C) BPCA analyses through systematic processing of multiple authentic standards with both fossil and modern 14C signatures at various concentrations. Using this approach, we precisely apportion the contribution of extraneous carbon with respect to the four implemented subprocedures. Assuming a constant source and quantity of extraneous carbon we correct and statistically evaluate uncertainties in resulting 14C data. Subsequently, we examine the results of triplicate analyses of reference materials representing four different environmental matrices (sediment, soil, aerosol, riverine natural organic matter) and apportion their BPCA sources in terms of carbon residues derived from biomass or fossil fuel combustion. This comprehensive approach to CSRA facilitates retrieval of robust 14C data, with application in environmental studies of the continuum of pyrogenic carbon.