This experimental study supports computational evidence that the excitation of d-band electrons have a significant impact on the material response of gold to an ultrashort laser pulse. A voltage biased Langmuir probe was used to detect the electron and positive ion emission from a 20 nm thick Au film at 343 nm, 515 nm and 1030 nm laser wavelengths. The laser wavelengths used provided photon energies above and below the interband transition threshold (ITT) for d-band excitation in gold (1.9 eV). Variations in optical properties of the Au film at different laser wavelengths were accounted for to ensure that comparisons were made at equal values of absorbed fluences. Data showed a significantly higher number of electrons emitted over a longer period when the energy of the incident photons exceeded the ITT. The electronic current generated at the probe indicated that the first electrons detected were primarily emitted via multiphoton photoemission. Electrons were also detected at later times when the photon energy exceeded the ITT and this was attributed to thermionic emission. The current generated from the positive ion emission was significantly lower than for electron emission, but indicated the formation of a plasma at a threshold fluence that increases with decreasing photon energy. (C) 2014 Elsevier B.V. All rights reserved.