A simple approach for synthesizing needle‐shaped α‐Ni(OH)2 nanoparticles adorned on graphene oxide, α‐Ni(OH)2‐GO, is described. The nanocomposite was isolated as an air‐stable black powder and characterized by various instrumental techniques. The interweaved needle‐shaped morphology and the average particle diameter ~7 nm of the adorned α‐Ni(OH)2 nanoparticles were ascertained by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) analysis, respectively. The catalytic potential of the nanocomposite was scrutinized in the synthesis of monosubstituted ketones via a hydrogen autotransfer strategy and synthesis of azines via dehydrogenative pathway. The products of both reactions were isolated in excellent yields and characterized by nuclear magnetic resonance (NMR) spectroscopy. α‐Ni(OH)2‐GO could be segregated and recycled for up to five cycles. The operational simplicity, broad substrate scope, non‐toxic side products, recyclability, and superior catalytic potential of the catalyst are some of the remarkable features of this protocol.