The X+ 2π΄+π’ ground electronic state of the Mg+2 ion has been studied by pulsed-field-ionization zero-kineticenergy (PFI-ZEKE) photoelectron spectroscopy. Rotationally cold Mg2 molecules produced in a laser-ablation supersonic-expansion source were ionized by resonant two-photon absorption from the X 1π΄+π (π£β²β² = 0) ground vibronic state. The photoelectron spectra of the π£+ = 3 β 14 vibrational levels of the X+ state were recorded with rotational resolution and their analysis led to the determination of accurate term values and rotational constants for these levels. Improved values of the adiabatic ionization energy of 24Mg2 (51 503.9(4) cmβ1) and of the ground-state dissociation energy of 24Mg+2 (10 572.3(6) cmβ1) were determined from experimental data.