The electronic and geometrical structure of a nitrogen-doped Al-6(-) cluster (Al6N-) is investigated using photoelectron spectroscopy and ab initio calculations. Photoelectron spectra of Al6N- have been obtained at three photon energies with seven resolved spectral features. The electron affinity of Al6N has been determined to be 2.58 +/- 0.04 eV. Global minimum structure searches for A(6)N(-) and its corresponding neutral form are performed using several theoretical methods. Vertical electron detachment energies, calculated using three different methods for the lowest energy structure and a low-lying isomer, are compared with the experimental data. The ground-state structure of Al6N- is established from the joint experimental and theoretical study to consist of an Al-2 dimer bonded to the top of a quasi-planar tetracoordinated N unit, Al4N-, or it can be viewed as a distorted trigonal prism structure with the N atom bonded in one of the prism faces. For neutral Al6N, three low-lying isomers are found to compete for the global minimum, two of which are built from the tetracoordinated Al4N unit. The chemical bonding in Al6N- is discussed on the basis of molecular orbital and natural bond analyses.