The ZrW2O8 family of materials has been shown to display the unusual property of an isotropic bulk contraction in volume as a function of temperature. We report here on negative thermal expansion properties and oxygen migration at very low temperatures in ZrW2-xMoxO8 phases. ZrWMoO8 shows significant negative thermal expansion (alpha(1) = -8.7 x 10(-6) K-1) and oxygen migration at temperatures as low as 200 K with an activation energy of 0.23 eV. We are unaware of oxygen migration at such low temperatures in other electronic insulators. The low-temperature migration is associated with an order-disorder transition between the a and beta forms of the material with Delta V-disorder = -0.24%. A negative volume change for an order-disorder transition is unusual.