Metal doping is an appealing modification strategy of graphitic carbon nitride (g-C3N4) to improve its photo-catalytic activity. The interactions of g-C3N4 precursors with metals, however, has often been underappreciated, which can induce great impacts on g-C3N4 formation and properties. Herein, the impacts of metals (Na, K, Ca, Mg) on the morphology, structure, and photoactivity of urea-derived g-C3N4 were investigated. Our TEM and XPS results confirmed that the interactions of doped metals with urea precursors lead to the incorporation of O atoms from urea molecules into the framework of g-C3N4. Due to the synergistic effects of the metals and structural O atoms, doped g-C3N4 performed an elevated photodegradation of antibiotics under the visible light irradiation, which was attributed to the enhanced light-harvesting and reduced charge recombination. In addition, the doped metals presented uneven regulation on the band structures and morphology of g-C3N4. As a result, both superoxide and hydroxyl radicals were generated by g-CN-Na and g-CN-K, whereas, only superoxide radicals were involved in g-CN, g-CN-Ca and g-CN-Mg. Consequently, diversified photodegradation mechanisms for enrofloxacin (ENR) were observed that the g-CN, g-CN-Ca and g-CN-Mg reaction systems mainly attacked the piperazine moiety of ENR while g-CN-Na and g-CN-K provided additional photodegradation pathway by attacking quinolone core of ENR. The present work could provide new insights into further understanding of doping chemistry with g-C3N4.