Eu3+ doped CdMoO4 super red emission phosphors with charge compensation were prepared by the traditional high temperature solid-state reaction method in air atmosphere. The interrelationships between photoluminescence properties and crystalline environments were investigated in detail. The 3D network structure which composed by CdO8 and MoO4 polyhedra can collect and efficiently transmit energy to Eu3+ luminescent centers. The relative distance between Eu3+ ions decreased and energy interaction increased sharply with the appearance of interstitial occupation of O2- ions ([Formula: see text]). Therefore, fluorescence quenching occurs at the low concentration of Eu3+ ions in the 3D network structure. Fortunately, the charge compensator will reduce the concentration of [Formula: see text] which can break the energetic interaction between Eu3+ ions. The mechanism of different charge compensators has been studied in detail. The strong excitation band situated at ultraviolet and near-ultraviolet region makes it a potential red phosphor candidate for n-UV based LED.