Temperature-dependent photoluminescence of structurally precise Au-25(SC8H9)(18) and Au-38(SC12H25)(24) monolayer-protected cluster (MPC) nanoparticles were studied using energy-resolved, intensity-integrated, and time-resolved spectroscopy. Measurements were carried out at sample temperatures spanning the range from 4.5 to 200 K following electronic excitation using 3.1 eV pulsed lasers. The integrated PL intensity for Au-25(SC8H9)(18) increased sharply by 70% as the sample temperature was increased from 4.5 to 45 K. The PL intensity was statistically invariant for temperatures between 45 and 65 K but was quenched when the sample temperature was raised above 65 K. For both MPC samples, the global PL emission included several components. Each PL component exhibited an increase in emission energy when the sample temperature was increased from 4.5 to 40 K. This unexpected behavior may imply that MPCs in the 1 nm domain have negative expansion coefficients. Quantitative analysis of PL emission energies and peak widths obtained at sample temperatures greater than 45 K indicated MPC nonradiative relaxation dynamics are mediated by coupling to low-frequency vibrations associated with the ligand shell that passivated the nanoclusters, which accounted for the low emission yields at high sample temperatures. Contributions from two different vibrational modes were identified: Au(I)-S stretching (200 cm(-1)) and Au(0)-Au(I) stretching (90 cm(-1)). Analysis of each PL component revealed that the magnitude of electronic-vibration coupling was state-specific, and consistently larger for the high-energy portions of the PL spectra. The total integrated PL intensity of the Au-25(SC8H9)(18) MPC was correlated to the relative branching ratios of the emission components, which confirmed decreased emission for recombination channels associated with strong electron-vibration coupling and high emission yields for low emission energies at low temperature. The efficient low-energy emission was attributed to a charge-transfer PL transition. This conclusion was reached based on the strong correlation between temperature-dependent intensity-integrated and time-resolved emission measurements that revealed an similar to 3.5-5.5 meV activation barrier to nonradiative decay. These findings suggest that nanoscale structure and composition can be modified to tailor the optical and mechanical properties and electronic relaxation dynamics of MPC nanostructures