The molecular orientation and microstructure of films of the high-mobility semiconducting polymer poly(N,N-bis-2-octyldodecylnaphthalene- 1,4,5,8-bis-dicarboximide2,6-diyl-alt-5,5-2,2-bithiophene) (P(NDI2OD-T2)) are probed using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. In particular a novel approach is used whereby the bulk molecular orientation and surface molecular orientation are simultaneously measured on the same sample using NEXAFS spectroscopy in an angle-resolved transmission experiment. Furthermore, the acquisition of bulk-sensitive NEXAFS data enables a direct comparison of the information provided by GIWAXS and NEXAFS. By comparison of the bulk-sensitive and surface-sensitive NEXAFS data, a distinctly different molecular orientation is observed at the surface of the film compared to the bulk. While a more "face-on" orientation of the conjugated backbone is observed in the bulk of the film, consistent with the lamella orientation observed by GIWAXS, a more "edge-on" orientation is observed at the surface of the film with surface-sensitive NEXAFS spectroscopy. This distinct edge-on surface orientation explains the high in-plane mobility that is achieved in top-gate P(NDI2OD-T2) field-effect transistors (FETs), while the bulk face-on texture explains the high out-of-plane mobilities that are observed in time-of-flight and diode measurements. These results also stress that GIWAXS lacks the surface sensitivity required to probe the microstructure of the accumulation layer that supports charge transport in organic FETs and hence may not necessarily be appropriate for correlating film microstructure and FET charge transport.