DCTB [(H3C)(3)C-p-Ph-CH=C(CH3)-trans-CH=C(CN)(2)] has recently advanced to the most promising matrix material for matrix-assisted laser desorption/ionization (MALDI) within material sciences. However, data that would allow the evaluation of the electron-transfer reactivity within a thermochemical framework are sparse. The present study reports the first-time determination of the ionization energy (IE) of DCTB applying photoelectron (PE) spectroscopy. The experimental IE (8.54 +/-0.05 eV) is in excellent agreement with the theoretical value of 8.47 eV, obtained by AM1 calculations. The same level of theory determines the electron affinity (EA) as 2.31 eV. Model analytes of known thermochemistry (phenanthrene [C14H10], anthracene [C14H10] and fluorofullerene [C60F46/48]) are used to bracket the electron-transfer reactivity within DCTB-MALDI. The formation of molecular ions of these analytes either is expected or is beyond the thermochemical accessibility of the DCTB matrix.