In summary, an efficient method for defluorinative cross-couplings of aliphatic aldehydes with trifluoromethyl styrenes has been developed. The facile installation of the difluoromethylene unit to an array of aldehyde structures provides an effective entry to this desirable functional group class. The substrate scope enables wide variation of the aldehyde reaction partner, and the protocol is amenable to gram-scale syntheses. The combination of a hindered 6,6'-disubstituted bipyridine ligand, 1,5-hexadiene as an additive, triethylsilyl chloride, and nanopowder zinc were key components of the optimized procedure. Experiments detailing a ring-opening / chain-walking cascade process with cyclopropanecarboxaldehyde lends support to the involvement of organonickel intermediates as key intermediates involved in C-C bond formation and illustrate important differences in mechanism that result from subtle changes in ligand and substrate structures. This work expands the use of simple alkenes in nickel-catalyzed reductive couplings of aldehydes and illustrates that bipyridine ligand frameworks enable unique reactivity in processes of this type when used in combination with simple diene additives.