Forty three vibronic levels of C2H2+, X 2Πu, with υ4=0–6, υ5=0–3, and K=0–4, lying at energies of 0–3520 cm-1 above the zero-point level, have been recorded at rotational resolution. These levels were observed by double resonance, using 1+1′ two-color pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy. The intermediate states were single rovibrational levels chosen from the à 1Au, 4ν3 (K=1–2), 5ν3 (K=1), ν2+4ν3 (K=0), and 47 206 cm-1 (K=1) levels of C2H2. Seven of the trans-bending levels of C2H2+ (υ4=0–3, K=0–2) had been reported previously by Pratt et al. [J. Chem. Phys. 99, 6233 (1993)]; our results for these levels agree well with theirs. A full analysis has been carried out, including the Renner-Teller effect and the vibrational anharmonicity for both the trans- and cis-bending vibrations. The rotational structure of the lowest 16 vibronic levels (consisting of the complete set of levels with υ4+υ5≤=2, except for the unobserved upper 2Πu component of the 2ν4 overtone) could be fitted by least squares using 16 parameters to give an rms deviation of 0.21 cm-1. The vibronic coupling parameter [variant_greek_epsilon]5 (about whose magnitude there has been controversy) was determined to be -0.02737. For the higher vibronic levels, an additional parameter, r45, was needed to allow for the Darling-Dennison resonance between the two bending manifolds. Almost all the observed levels of the υ4+υ5=3 and 4 polyads (about half of the predicted number) could then be assigned. In a final fit to 39 vibronic levels with υ4+υ5≤=5, an rms deviation of 0.34 cm-1 was obtained using 20 parameters. An interesting finding is that Hund’s spin-coupling cases (a) and (b) both occur in the Σu components of the ν4+2ν5 combination level. The ionization potential of C2H2 (from the lowest rotational level of the ground state to the lowest rotational level of the cation) is found to be 91 953.77±0.09 cm-1 (3σ). [ABSTRACT FROM AUTHOR]