We have determined for the Bolivian Andes that the new global gravity models derived from the Gravity field and steady-state Ocean Circulation Explorer (GOCE) satellite mission may be used directly to study lithospheric structure. Toward this end, we have formulated Bouguer and isostatic gravity anomalies in spherical approximation, rather than in the usual planar approach, using spherical harmonic series consistent with the satellite-derived gravitational models. From the approximate equivalency of topographic masses and surface density layers using the Helmert condensation method we further derived and used isotropic transfer relations between the spherical spectra of topographic loads and elastic spherical shell deflections, where the Airy isostatic compensation is the special case of no flexural rigidity. A numerical comparison of these spherical harmonic models to conventional three-dimensional modeling based on topographic data and newly acquired surface gravity data in Bolivia confirmed their suitability for lithospheric interpretation. Specifically, the relatively high and uniform resolution of the satellite gravitational model (better than 83 km) produces detailed maps of the isostatic anomaly that clearly delineate the flexure of the Brazilian shield that is thrust under the Sub-Andes. Inferred values of the thickness of Airy-type roots and the flexural rigidity of the elastic lithosphere agree reasonably with published results based on seismic and surface gravity data. In addition, a local minimum in the flexural rigidity is evident at the sharp bend of the eastern margins of the Sub-Andes in Bolivia. This feature is consistent with earlier theories for counter rotations about a vertical axis at this minimum, associated with the confluence of the subducted Nazca plate and the Brazilian craton. The GOCE model thus generates high-resolution isostatic anomaly maps that offer additional structural detail not seen as clearly from previous seismic and gravity investigations in this region.