Three series of poly(ionic) carbosilane dendrimers peripherally functionalized with imidazolium groups substituted on N-3 with methyl, isopropyl and 2,6-diisopropylphenyl (Dipp) were prepared up to the 3rd generation together with model monovalent imidazolium iodides and used as N-heterocyclic carbene (NHC) precursors. Catalytic activity of model and dendritic NHCs generated in situ by deprotonation with DBU was tested in redox esterification of α,β-unsaturated aldehydes and the influence of substitution, dendrimer generation, temperature and substrate structure on the reaction outcome was evaluated. Dipp substituted NHCs showed high activity and selectivity in the reaction with primary alcohols. Effectiveness of organic solvent nanofiltration for the recycling of dendritic NHCs was demonstrated on the 1st generation Dipp substituted catalyst in model redox esterification of cinnamaldehyde with benzyl alcohol. A marked increase in both activity and selectivity in the first four reaction runs was observed and this improved performance was preserved in the following catalytic cycles.