So I’ve estimated that the Free Cities are probably somewhere around 15-20 million altogether. I would guess that the population of Slaver’s Bay is around 3-5 million. The Dothraki are probably 10 million altogether, given that Vaes Dothrak is supposed to be 10x the size of Pentos. Qarth is pretty big, probably 500k-1 million people.
So Essos up to where we’ve seen it (and remember we’ve only seen about ½ of the landmass) is around 28-36 million people?