<p>Chan-Lam coupling represents one of the most reliable methods for constructing C(sp²)−N bonds under mild conditions. However, application of this technology as a general platform for C(sp³)−N bond assembly remains a longstanding challenge due to the inherent limitation in boron-to-copper transmetalation. In contrast to the conventional two-electron process, the rapid capture of alkyl radicals by copper(II) complex affording the reactive high-valent copper(III) intermediate, has become a key part of the emerging approaches to forge C(sp³)−N bonds. Here, we report an <i>N</i>-alkylation protocol that overcomes the limitations of Chan-Lam coupling by using versatile alkylboronic pinacol esters (APEs) as radical precursors via aminyl radical-mediated boron abstraction. This distinct approach enables a versatile <i>N</i>-alkylation applicable to a wide range of APEs and <i>N</i>-nucleophiles with diverse functional groups. Synthetic utility of this protocol is further demonstrated by its ease of scalability, sequential <i>N</i>-alkylation of substrate with multiple reactive sites, and the late-stage modification of several complex bioactive materials.</p>