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The time-resolved emission spectra of the tetranuclear clusters Cu414(py-X)4 (X = H, 3-CI, 4-Ph, 4-PhCH2, or 4-But) at 296 K in toluene each display separate, uncoupled emissions from two states, a short-lived (0.13-0.56 p) metal-to-ligand charge transfer in the range 473-537 nm and a much more intense and longer lived (10-13 p) metal cluster centred (MCC) emission in the range 678-698 nm; for X = 4-Ph the MCC emission exhibits an unusual, temperature dependent rise-time.