The 29-year-old 15th seed had never before even reached a Masters 1000 semi-final.
In Sunday's final, he will play the winner of the second semi-final between nine-time winner Rafael Nadal, the fourth seed, and number 10 David Goffin of Belgium.
Ramos-Vinolas carried on the momentum he gained in knocking out top seed Andy Murray in the third round and fifth seed Marin Cilic in the quarters, with the slightly less notable scalp of 11th seed Pouille.
The Spaniard, who saved seven of nine break points, had come to the principality with only three previous victories from 29 matches against top 10 opponents.
Of the four semi-finalists, only Nadal had previously reached a Masters level semi-final.