Based on 10 shale samples collected from 4 wells in Qinshui Basin, we investigate the full-sized pore structure and fractal characteristics of Marine-Continental transitional shale by performing organic geochemistry, mineralogical composition, Nitrogen gas adsorption (N2 adsorption) and Nuclear Magnetic Resonance (NMR) measurements and fractal analysis. Results show that the TOC content of the shale samples is relatively high, with an average value of 2.44wt%, and the thermal evolution is during the mature-over mature stage. The NMR T2 spectrum can be used to characterize the full-sized pore structure characteristics of shale. By combining N2 adsorption pore structure parameters and NMR T2 spectrums, the surface relaxivity of samples are calculated to be between 1.7877 um/s and 5.2272 um/s. On this basis, the T2 spectrums are converted to full-sized pore volume and surface area distribution curves. The statistics show that the pore volume is mainly provided by mesopore, followed by micropore, and the average percentages are 65.04% and 30.83% respectively; the surface area is mainly provided by micropore, followed by mesopore, and the average percentages are 60.8004% and 39.137% respectively; macropore contributes little to pore volume and surface area. The pore structure characteristics of shale have no relationship with TOC, but strong relationships with clay minerals content. NMR fractal dimensions Dmicro and Dmeso have strong positive relationships with the N2 adsorption fractal dimensions D1 and D2 respectively, indicating that Dmicro can be used to characterize the fractal characteristics of pore surface, and Dmeso can be used to characterize the fractal characteristics of pore structure. The shale surface relaxivity is controlled by multiple factors. The increasing of clay mineral content, pore surface area, pore surface fractal dimension and the decreasing of average pore size, will all lead to the decreasing of shale surface relaxivity.