Sn2Nb2−xTaxO7 (x = 0.0–2.0) with pyrochlore structure is a promising material for p-type oxide semiconductors. A systematic study of its Nb/Ta ratio indicated that the hole–generation efficiency of the Nb end (Sn2Nb2O7) was an order of magnitude lower than that of the Ta end (Sn2Ta2O7). Although this occurs due to differences in oxygen-vacancy formation, the origins of the hole–generation efficiencies remain unclear due to limited information on local and global crystal-structure disorders in pyrochlore Sn2Nb2O7 and Sn2Ta2O7. In this study, the crystal structures of Sn2B2O7 (B = Nb, Ta), composed of BO6 octahedra and Sn4O tetrahedra, were investigated using X-ray absorption spectroscopy and X-ray diffraction. A detailed investigation of the local and global crystal structures indicated a larger amount of disorder in the Sn4O tetrahedra in Sn2Nb2O7 compared to Sn2Ta2O7; disorder in the BO6 octahedra occurred only in Sn2Ta2O7. This study indicates that an appropriate selection of the B-site element is vital for suppressing defect and disorder formation in Sn4O tetrahedra and subsequently improving the hole–carrier–generation efficiency.