Nickel cation-acetylene complexes of the form Ni+(C2H2)(n) Ni+(C2H2)Ne, and Ni+(C2H2)(n)Ar-m (n = 1-4) are produced in a molecular beam by pulsed laser vaporization. These ions are size-selected and studied in a time-of-flight mass spectrometer by infrared laser photodissociation spectroscopy in the C-H stretch region. The fragmentation patterns indicate that the coordination number is 4 for this system. The n = 1-4 complexes with and without rare gas atoms are also investigated with density functional theory. The combined IR spectra and theory show that T-complexes are formed for the n = 1-4 species, causing the C-H stretches in the acetylene ligands to shift to lower frequencies. Theory reveals that there are low-lying excited states nearly degenerate with the ground state for all the Ni+(C2H2)n complexes. Although isomeric structures are identified for rare gas atom binding at different sites, the attachment of rare gas atoms results in only minor perturbations on the structures and spectra for all complexes. Experiment and theory agree that multiple acetylene binding takes place to form low-symmetry structures, presumably due to Jahn-Teller distortion and/or ligand steric effects. The fully coordinated Ni+(C2H2)(4) complex has a near-tetrahedral structure.