There were many queens, female monarchs and other women who were leaders in countries as far back as written history goes. Ancient Rome had a few empresses like Faustina, Truchilla and Pulchera for example. read more
It's very hard to point out the very first queen of a Nation in world history, but there is a wikipedia page that lists queen reigns from the earliest known to present day: List of queens regnant - Wikipedia. read more
The first recorded king and queen in history are King Narmer (also known as King Menes) and his co-ruler Queen Nthotep. They ruled in Ancient Egypt, 3407 to 3346 B.C., as the First Dynasty of Upper and Lower Egypt. read more