In this article, we disclose the design, synthesis and reactivity of a bismuth REC (4), featuring a weak Bi-O bond. The facile homolysis at room temperature leads to a highly reactive Bi(II) (5) with unusual chemical properties. Compound 4 is able to perform a rapid, selective and mild activation of ammonia and water-among other ammines and alcohols-resulting in exclusive alkoxy-and amido-bismuth(III) complexes. Reactivity studies of the novel Bi(III)-NHR resulted in engagement with the triad of proton, hydride or radical hydrogen sources, a rather unique feature for main group elements. A combined experimental and computational analysis of the system suggests that upon homolysis, coordination of the lone pair in X-H to 5 occurs, resulting in a dramatic reduction of the BDFEX-H and allowing its cleavage by the phenolate radical. Although Bi(III)-NHR have shown reactivity involving the ligand framework, deuteration experiments and kinetic analysis indicate that no element-ligand cooperation occurs during the activation, in agreement with the mechanistic hypothesis from a computational analysis. Properties such as coordination-induced bond weakening at bismuth combined with the rich reactivity pattern offered by the Bi(III)-amido complexes (at metal and ligand), could open the door to new possibilities for the conversion of cheap and abundant alcohols and ammines into high-value compounds.