Engineerings of facet exposure, nonstoichiometric defects and morphology are the key parameters affecting the SnO2 performance. Development of synthetic procedures enabling to control all these variables in one pot towards enhanced physicochemical performance is a big challenge. Herein we report such a facile microwave hydrothermal preparation of 3D hierarchical architecture assembled from single-crystalline nonstoichiometric SnO2 (denote as SnO2-δ) nanosheets with self-doped Sn2+ and controllably exposed {101} facets. Polyvinylpyrrolidone (PVP) is used as capping agent allowing to stabilize the ultrathin and ultra-large SnO2-δ nanosheets and avoid their dissolution in the highly alkaline environment due to the introduction of highly concentrated NaOH, which together with PVP contribute to the formation of nanosheet morphology with preferential growth plane (121) and dominant reactive {101} surfaces. The detailed structural characteristics are examined by XRD, SEM, TEM, FTIR, XPS and Mössbauer spectroscopy, revealing that SnO2-δ contains 17 at.% of Sn2+ dopant. These nonstoichiometric SnO2-δ hierarchical architectures capped with carbonized PVP manifest superior lithium storage properties compared with the stoichiometric SnO2, owing to the novel open hierarchical structure composed of flexible and ultrathin nanosheets with large surface area (82m2/g) and carbon-coating, which avoid the aggregation and provide porous channels facilitating the diffusion of electrolyte and lithium ions.