CW and pulsed ENDOR was used to probe the electron nuclear superhyperfine interactions between V
4+ ions and distant Sn nuclei in vanadium doped tin oxide (V/SnO
2). Whilst interactions with two sets of nearest neighbour Sn nuclei (with a V–Sn distance of 3.185 and 3.708 Å respectively) are observed by EPR, superhyperfine couplings to two remote sets of tins (with a V–Sn distance of 6.370 and
7.42 Å) are detected by ENDOR. The interaction was found to be largely isotropic and largest along the crystal
c axis. Small differences in the remote tin environments were also detected by ENDOR.