The [Ir(df-ppy) 2 (ptb)] + complex (where df-ppy = 2-(2,4-difluorophenyl)pyridine anion; ptb = 1-benzyl-1,2,3-triazol-4-ylpyridine) has previously been shown to be a promising blue luminophore for electrogenerated chemiluminescence (ECL). Herein, we examine the ECL of three [Ir(df-ppy) 2 (ptb)] + derivatives (containing df(CF 3 )-ppy-Me, df(CN)-ppy, or df-ppy-CF 3 ligands) in comparison with the parent complex. In the annihilation mode, all four complexes exhibited ECL, although the emission from [Ir (df(CN)-ppy) 2 (ptb)] + was weak and red-shifted from its photoluminescence. The absence of this shift in the corresponding reductive-oxidation co-reactant ECL with benzoyl peroxide (BPO), and the very low ECL intensity in oxidative-reductive coreactant ECL with tri-n-propylamine (TPrA) enables this effect to be ascribed to oxidative degradation. The [Ir(df-ppy-CF 3 ) 2 (ptb)] + complex gave the greatest ECL intensities of the four [Ir ðC^NÞ 2 (ptb)] + complexes in the annihilation mode and through both co-reactant pathways, and shows great potential as a blue electrochemiluminophore. In "mixed annihilation" ECL experiments involving the oxidation of Ir(ppy) 3 and the reduction of the [IrðC^NÞ 2 (ptb)] + complexes, only [Ir(df-ppy) 2 (ptb)] + and [Ir (df(CF 3 )-ppy-Me) 2 (ptb)] + elicited the green ECL from Ir(ppy) 3 *, as the electron-withdrawing substituents on the other two complexes lower the SOMO energy of the reduced complexes below that required to attain the Ir(ppy) 3 * excited state upon reaction with [Ir(ppy) 3 ] + . Scheme 1. TPrA co-reactant ECL mechanism in which both the metal complex (M) and co-reactant are electrochemically oxidized. [4a] Alternative pathways, including one in which only the co-reactant is oxidized, [4b] have also been identified. The feasibility of these pathways for any metal complex electrochemiluminophore can be predicted from the reduction potentials and emission energy of the complex. [4c] ChemElectroChem Articles