<jats:title>Abstract</jats:title><jats:p>The iridium‐catalyzed highly regioselective transfer hydrogenation of a variety of 2‐substituted and 2,9‐disubstituted 1,10‐phenanthrolines under mild conditions with formic acid as the hydrogen source is described. In the presence of a catalytic amount of the iridium complex [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub>, the transfer hydrogenation proceeded smoothly in 1,4‐dioxane under ligand‐free conditions, exclusively leading to a range of 1,2,3,4‐tetrahydro‐1,10‐phenanthroline products in high yields. The catalyst generated <jats:italic>in situ</jats:italic> from [Cp*IrCl<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub> and (<jats:italic>R</jats:italic>,<jats:italic>R</jats:italic>)‐(CF<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>C<jats:sub>6</jats:sub>H<jats:sub>3</jats:sub>SO<jats:sub>2</jats:sub>‐dpen [<jats:italic>N</jats:italic>‐(2‐amino‐1,2‐diphenylethyl)‐3,5‐bis(trifluoromethyl)benzenesulfonamide] could efficiently catalyze the asymmetric transfer hydrogenation of these 1,10‐phenanthrolines in isopropyl alcohol (<jats:italic>i‐</jats:italic>PrOH) to afford chiral 1,2,3,4‐tetrahydro‐1,10‐phenanthrolines in high yields with up to >99% <jats:italic>ee</jats:italic>. The key to the success of the reduction is the choice of solvent and hydrogen source.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/gif" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/mcontent.gif"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text></jats:p>