The kinetics of encounters between the pyrene pendants randomly attached along a polystyrene chain (Py-PS) were monitored with a fluorescence blob model (FBM) as an external quencher was added to the solution to decrease the lifetime of the excited pyrene. The fluorescence decays acquired with the Py-PS samples yielded a measure of the volume V-blob probed by an excited pyrene during its lifetime in the form of N-blob(o), the number of monomers found within V-blob, and k(blob)(o), which is inversely proportional to V-blob. Both N-blob(o) and k(blob)(o-1) were found to increase with increasing probing time as the excited pyrene was allowed to probe a larger V-blob volume. The rate constant for pyrene-pyrene encounters was obtained from the product < k(blob)N(blob)>. < k(blob)N(blob)> was found to decrease with increasing probing time, in agreement with scaling arguments suggesting that, as the probing time increases, the excited pyrene probes a larger V-blob where the local concentration of ground-state pyrenes in the polymer coil, [Py](loc), is smaller. k(blob)(o), which is inversely proportional to V-blob, was found to scale as N-blob(o alpha), where alpha equaled -1.5 and -1.2 in DMF and THF, respectively. The alpha exponents found for the Py-PS samples are in the same range as those found for other polymers exhibiting a random polymer coil conformation in solution and were much smaller than those obtained with more compact structured alpha(-)helical polypeptides randomly labeled with pyrene. Master curves were also constructed that describe how k(blob)(o) and the product < k(blob)N(blob)> scale as a function of solvent viscosity, probing time, and N-blob(o). These scaling laws illustrate the opposite effects that probing time and viscosity have on N-blob(o), V-blob(o), and the product < k(blob)N(blob)>.