A detailed study of the structure-composition-properties correlation is reported for the as-prepared (AP) and two oxygenated (oxygenation carried out at ambient pressure and under high pressure) Mo0.3Cu0.7Sr2ErCu2Oy samples. Their crystal structures were characterized by combining the x-ray/neutron powder diffraction (NPD) and electron diffraction techniques. All the samples show tetragonal symmetry, crystallizing in the P4/mmm space group. The influence of oxygenation in the electronic states for the Mo0.3Cu0.7Sr2ErCu2Oy system associated with an oxidation reaction leading from a non-superconducting to a superconducting state has also been investigated by means of x-ray photoelectron spectroscopy (XPS). XPS measurements show the predominance of the MoV oxidation state over the MoVI one in the AP sample; annealing under flowing oxygen enhances both the MoVI and CuII amounts. The AP sample shows the existence of ferromagnetic clusters originated from the short-range magnetic correlations of the paramagnetic MoV cations. On the other hand, all the oxygenated samples are not magnetic but superconducting. The high-pressure oxygenated sample shows the highest superconducting transition temperature of TC = 84 K. A partial oxygen ordering in the (Mo/Cu)O1+δ chain and a decrease in the charge transfer energy after oxygenation induces superconductivity in the oxygenated samples.