A water-soluble porphyrinato ytterbium complex linked with rhodamine B (Yb-2) showed mitochondriaspecific subcellular localization and strong two-photoninduced NIR emissions (lambda(em) = 650 nm, porphyrinate ligand pi -> pi* transition; lambda(em) = 1060 nm, Yb(III) (5)F(5/2) -> (5)F(7/2) transitions; sigma(2) = 375 GM in DMSO) with an impressive Yb(III) NIR emission quantum yield (1% at lambda(ex) = 340 nm; 2.5% at lambda(ex) = 430 nm) in aqueous solution.