Acetylene cations [HCCH]+ produced in the A2Σ+g state by extreme ultraviolet (XUV) photoionization are investigated theoretically, based on a mixed quantum-classical approach. We show that the decay of the A2Σ+g state occurs via both ultrafast isomerization and nonradiative electronic relaxation. We find a time scale for hydrogen migration and electronic decay of about 60 fs, in good agreement with recent XUV-pump/XUV-probe time-resolved experiments on the same system [Phys. Rev. Lett. 105, 263002 (2010)]. Moreover, we predict an efficient vibrational energy redistribution mechanism that quickly transfers excess energy from the isomerization coordinates to slower modes in a few hundred femtoseconds, leading to a partial regeneration of acetylenelike conformations.