If all your devices under development live on that ESD mat, and every time you start working, you connect yourself to the mat first, then theoretically this will work: everything's on the same potential. But this is a very small island.
In reality, people move around, and equipment moves around. In a perfect setting, everything would be slightly conductive, and connected to the same reference - which, logically, will be the actual ground as in the soil around the building. So you want to make the "island" as large as possible.
By connecting your ESD mat to the mains protective earth, you are closer to that ideal, with the least amount of work, building materials such as concrete being very slightly conductive.
In a more professional setting, using more controlled conductivity in building materials - such as ESD floor tiling etc. - becomes important. They are still referenced to the actual earth, to maximize the "island" and remove places where large static discharges would occur.