Two different classes of ruthenium complexes, namely, [1-mesityl-3-(2,6-Me₂-phenylacetamido)-imidazol-2-ylidene]Ru(p-cymene)Cl (1c) and {[1-(pyridin-2-ylmethyl)-3-(2,6-Me₂-phenyl)-imidazol-2-ylidene]Ru(p-cymene)Cl}Cl (2c), successfully catalyzed the one-pot tandem alcohol–alcohol coupling reactions of a variety of secondary and primary alcohols, in moderate to good yields of ca. 63–89%. The mechanistic investigation performed on two representative catalytic substrates, 1-phenylethanol and benzyl alcohol using the neutral ruthenium (1c) complex showed that the catalysis proceeded via a partially reduced CC hydrogenated carbonyl species, [PhCOCH₂CH₂Ph] (3′), to the fully reduced CO and CC hydrogenated secondary alcohol, [PhCH(OH)CH₂CH₂Ph] (3). Furthermore, the time dependent study showed that the major product of the catalysis modulated between (3′) and (3) during the catalysis run performed over an extended period of 120 hours. Finally, the practical utility of the alcohol–alcohol coupling reaction was demonstrated by preparing five different flavan derivatives (13–17) related to various bioactive flavonoid natural products, in a one-pot tandem fashion.