We studied the behavior of porous carbon compressed by laser-generated shock waves. In particular, we developed a new design for targets, optimized for the investigation of carbon reflectivity at hundred-GPa pressures and eV/k temperatures. Specially designed “two-layer-two materials” targets, comprising porous carbon on transparent substrates, allowed the probing of carbon reflectivity and a quite accurate determination of the position in the P, T plane. This was achieved by the simultaneous measurement of shock breakout times, sample temperature (by optical pyrometry) and uid velocity. The experiments proved the new scheme is reliable and appropriate for reflectivity measurements of thermodynamical states lying out of the standard graphite or diamond hugoniot. An increase of reflectivity in carbon has been observed at 260 GPa and 14,000 K while no increase in reflectivity is found at 200 GPa and 20,000 K. We also discuss the role of numerical simulations in the optimization of target parameters and in clarifying shock dynamics.