The telomerization reaction of dienes with alcohols mediated by organopalladium complexes represents a versatile method to convert butadiene into value-added chemicals. In this contribution, we have examined the catalytic behavior of a series of well-defined palladium N-heterocyclic carbene precatalysts (Pd-NHC) in the telomerization of butadiene with ethanol. The bulky and less sterically demanding NHC ligands greatly influence yields and selectivity towards the linear product. With more hindered NHC ligands, the branched product is obtained in unprecedented higher amounts. The telomerization of butadiene with the renewable solketal leads to selective and complete conversion to product in minutes.