The local environments around tellurium atoms in a series of tellurium oxide crystals were probed by Te-125 solid-state NMR spectroscopy. Crystals with distinct TeOn units (n from 3 to 6), including Na2TeO3, alpha-TeO2 and gamma-TeO2, Te2O(PO4)(2), K3LaTe2O9, BaZnTe2O7, and CsYTe3O8 were studied. The latter four were synthesized through a solid-state process. X-ray diffraction was used to confirm the successful syntheses. The Te-125 chemical shift was found to exhibit a strong linear correlation with the Te coordination number. The Te-125 chemical-shift components (delta(11), delta(22), and delta(33)) of the TeO4 units were further correlated to the O-Te-O-bond angles. With the aid of Te-125 NMR, it is likely that these relations can be used to estimate the coordination states of Te atoms in unknown Te crystals and glasses.