**No enzyme** is involved in base-pairing (annealing).
This **does** happens by **chance** , but the chances are governed by **stoichiometric** considerations.
The main such consideration is that the (low molecular weight) _primers are added at a high concentration_ (greater than that of the DNA) and therefore have a greater chance of encountering the appropriate region of the DNA than its complementary strand does. (Reannealing of the denatured DNA strands _can_ occur, but not over the time period of PCR.)