We present a versatile nickel-electrocatalytic deaminative cross-coupling platform for the efficient construction of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds from readily available alkyl bistriflimides. This methodology involves the assembly of two leaving groups on alkyl amines to form alkyl bistriflimides, followed by their effective coupling with a wide range of alkyl halides, alkyl pseudohalides, aryl halides, and alkenyl halides under electrochemical reductive conditions. Moreover, the successful application of electrochemical reductive relay cross-coupling and transition metal-free cross-electrophile coupling further demonstrates the versatility of alkyl bistriflimides as valuable building blocks in organic synthesis. Combined control experiments and density functional theory calculations provide insights into the reaction pathway and the crucial role of iodide in the catalytic process.