Experimental measurements of the one-bond scalar coupling of Cp2WH2 in tetrahydrofuran ((1)J(WH) = 73.4 Hz and (1)J(WC) = 4.8 Hz) are compared to density functional theory calculations of the same based upon geometries minimized utilizing a variety of approximate functionals typically utilized to calculate organometallic geometries. One difference between the various functionals is the Cp-W distance, and d(CpW) is linearly correlated to the calculated values for both (1)J(WH) and (1)J(WC). Differences in the structures of the Cp2WH2 reported in the literature are compared to the calculated geometries, utilizing calculated values of (1)J(WH) to provide insight into the differences. The distance between the tungsten and attached hydride as well as the angle of the cyclopentadienyl plane with respect to the tungsten cyclopentadienyl centroid vector also have a strong effect on (1)J(WH). A natural bond orbital (NBO) analysis of the orbital origins of (1)J(WH) indicates that the W-H sigma-bonding orbital is the primary contributor to the coupling constant.