Rhenium and osmium in organic-rich sedimentary rocks are dominantly hydrogenous, but any nonhydrogenous component will influence the accuracy and precision of the Re–Os date obtained. To minimize the influence of any nonhydrogenous Re and Os, we evaluate analysis of isolated organic matter from the whole rock, together with whole rock analysis using a CrO3–H2SO4 digestion medium instead of inverse aqua regia, for a black shale unit of the Exshaw Formation, Canada. This unit previously returned a whole rock Re–Os date of 358±10 Ma (Model 3) [Geochim. Cosmochim. Acta (2002)] using inverse aqua regia dissolution. Organic matter isolated from the whole rock matrix using the HF–BF3 technique [Org. Geochem. 20 (1993) 249] yields scattered data and a Re–Os date of 449±220 Ma (Model 3, MSWD=616). The organic matter analyses show similar 187Os/188Os values, but significantly lower 187Re/188Os values in comparison to the whole rock analyses. We show that the Re–Os systematics of organic matter are altered during chemical isolation, and as such we suggest that the HF–BF3 method should not be used for Re–Os analysis of organic matter. Whole rock Re–Os analysis using a CrO3–H2SO4 digestion medium yields significantly better regression analysis compared with the inverse aqua regia method, and the Re–Os data identify two distinct initial 187Os/188Os values for the sample set. Separate regressions of these data yield precise dates [366.1±9.6, MSWD=2.2 and 363.4±5.6 Ma, MSWD=1.6 (Model 3)], which are indistinguishable from the age constraints for this formation (363.4±0.4 Ma, U–Pb monazite). Comparison of the Re–Os dates obtained from aqua regia and CrO3–H2SO4 methods suggests that the former may contain nonhydrogenous Re and Os, whereas the CrO3–H2SO4 method dominantly liberates hydrogenous Re–Os from organic matter, allowing for better stratigraphic age determinations and evaluation of the Os isotope composition of seawater.