A detailed study of the structure and properties for the as-prepared and oxygen annealed Mo0.3Cu0.7Sr2TmCu2Oy material is reported. The Cu/Mo cationic distribution is established using a combination of x-ray/neutron powder diffraction refinement. The chemical substitution of the Mo ions for the Cu ions in the CuYSr2Cu2O(7-δ) structure is found to occur in both of the copper sites for the as-prepared sample. Interestingly, no trace of Mo substitution in the copper plane site is found to occur after oxygenation. The as-prepared Mo0.3Cu0.7Sr2TmCu2Oy material is found to be a spin glass (SG) system and explained on the basis of the cluster-by-cluster freezing model. On the other hand, the oxygen annealed material is superconducting (SC) (T(SC,onset) = 31 K). A peak has been observed in the critical current density plot and can be explained on the basis of field induced pins. The influence of oxygen annealing in the structure and properties of this material are presented and discussed. This seems to be the first case of a SG-SC transformation following an oxidation reaction in cuprates.