How an ESD mat should operate:
multilayer:
* the top layer is relatively high ohmic. It prevents high current flow when a PCB is placed on the mat with line voltage applied. --> no smoke
It also reduces ESD currents due to its high impedance.
* then there is a higher conductive layer. It is used to lead ESD currents to the earth connection. It also keeps areas of high potential small on the top layer (this prevents you from being electrocuted).
--> both layers help to keep ESD damage low: Low currents, relatively fast voltage decay, small areas, currents fed to GND.
* Maybe there is an additional layer (at the bottom) between this higher conductive layer and the desktop surface. It depends on the mat.