Using vacuum-ultraviolet (VUV) synchrotron radiation, threshold and dissociative photoionization of cyanopropyne (CH3C3N) in the gas phase have been studied from 86 000 cm−1 up to 180 000 cm−1 by recording Threshold-PhotoElectron Spectrum (TPES) and PhotoIon Yield (PIY). Ionization energies of the four lowest electronic states X̃+2E,Ã+2A1,B̃+2E and C̃+ of CH3C3N+ are derived from the TPES with a better accuracy than previously reported. The adiabatic ionization potential of CH3C3N is measured as 86872±20 cm−1. A description of the vibrational structure of these states is proposed leading to the first determination of the vibrational frequencies for most modes. The vibrational assignments of the X̃+ state are supported by density functional theory calculations. In addition, dissociative photoionization spectra have been recorded for several cationic fragments in the range 12–15.5 eV (96 790–125 000 cm−1) and they bring new information on the photophysics of CH3C3N+. Threshold energies for the cationic dissociative channels leading to CH2C3N+, CHC3N+, HC3H+, HCNH+ and CH3+ have been measured for the first time and are compared with quantum chemical calculations.