In summary, we have developed a selective Ni(0)-catalyzed hydroalkylation of non-conjugated dienes directly involving the α-hydrogen atom of ketones via a LLHT or Ni-hydride formation pathway. The method converts ketones and non-conjugated dienes -both convenient, cheap and widely accessible starting materials -to highly valuable α-allylated products in excellent yields. The transformation creates adjacent quaternary and tertiary stereogenic centers in a diastereoselective manner. In addition, the design of a novel chiral bulky NHC ligand enabled to conduct the reaction in an enantioselective manner providing the functionalized products with up to 99:1 er. Notably, the whole process is fully atom-economic. This contrasts typical carbonyl α-functionalizations with precious metals that require pre-functionalized substrates, the enolate nucleophile (ketone with base) and allyl electrophile. The mild reaction conditions are enabled by a bulky designer NHC ligand. Especially, we have observed a strong relevance of the substituent on the para-position of the flanking aryl groups, tentatively influencing the reductive elimination step. Surprisingly, modifications at this position were so far largely neglected in N,N-diaryl-based NHC ligands. Computational studies confirm a probable LLHT process from the ketone substrate to the olefin as initial step which as well sets the diastereoselectivity of the whole transformation. A β-hydride elimination chain walking followed by reductive elimination of a formed π-allyl species lead to the observed products. We anticipate that the demonstrated facile activation of α-C-H bond of carbonyl groups by this Ni(0)NHC system can be paired with a broad range various π-unsaturations and exploited in the future for a stereoselective and efficient general access to valuable chiral functionalized ketones by sustainable 3d-metal catalysis.