Morphologically, ants of this species are similar to the Mexican Polyergus topoffi, but have narrower heads and petioles and the first tergites of their gasters are more hairy.

[2] P. rufescens is native to parts of Europe including Spain, France, the Netherlands, Germany, Switzerland, Austria, Bulgaria, Italy, Croatia, Serbia, and Slovenia.

The host species vary in different parts of the range and include F. cunicularia, F. fusca, F. rufibarbis, F. clara, F. gagates, and F. cinerea.

[6] Huber experimentally put 30 of the slave-making ants in a box with some of their larvae, some pupae, a little soil, and a generous supply of honey.

It very soon "established order, formed a chamber in the earth, gathered together the larvae, extricated several young ants that were ready to quit the condition of pupae, and preserved the life of the remaining Amazons.

Observations on the ground show that the female makes certain movements of her mandibles just before mating, and this is thought to release a sexually attractive pheromone.

The majority join a slave raid within a few days of mating, but only some of these attempt to infiltrate the target colony, others returning home with the raiders.

She may join a column of raiding ants and use the panic and confusion surrounding their attack on the target colony to infiltrate the nest.