Few-photon induced ultrafast dynamics in acetylene (C2H2) leading to several dissociation channels—deprotonation (H++C2H+ and H++C2H2+), symmetric break-up (CH++CH+) and isomerization (C++CH2+)-–were investigated employing the (XUV; extreme ultra-violet)-pump–(XUV; extreme ultra-violet)-probe scheme at the free-electron laser in Hamburg, combined with multi-hit coincidence detection. The kinetic energy releases and fragment-ion momentum distributions for various decay channels are presented. The C++CH2+ and H++C2H2+ channels reveal clear signatures of ultrafast molecular mechanisms, demonstrating potential applications of our pump-probe technique to complex systems in order to study a large variety of ultrafast phenomena in the XUV regime.