This paper presents the sample return mission to a primitive Near-Earth Asteroid (NEA) MarcoPolo-R proposed to the European Space Agency in December 2010. MarcoPolo-R was selected in February 2011 with three other missions addressing different science objectives for the two-year Assessment Phase of the Medium-Class mission competition of the Cosmic Vision 2 program for launch in 2022. The baseline target of MarcoPolo-R is the binary NEA (175706) 1996 FG3, which offers an efficient operational and technical mission profile. A binary target also provides enhanced science return. The choice of a binary target allows several scientific investigations to occur more easily than through a single object, in particular regarding the fascinating geology and geophysics of asteroids. MarcoPolo-R will rendezvous with a primitive, organic-rich NEA, scientifically characterize it at multiple scales, and return a bulk sample to Earth for laboratory analyses. The MarcoPolo-R sample will provide a representative sample from the surface of a known asteroid with known geologic context, and will contribute to the inventory of primitive material that is probably missing from the meteorite collection. The MarcoPolo-R samples will thus contribute to the exploration of the origin of planetary materials and initial stages of habitable planet formation, to the identification and characterization of the organics and volatiles in a primitive asteroid and to the understanding of the unique geomorphology, dynamics and evolution of a binary asteroid that belongs to the Potentially Hazardous Asteroid (PHA) population.