The heterogeneous catalytic polymerization of styrene vapor with a tetrakis(acetonitrile)palladium(II) tetrafluoroborate, [Pd(CH3CN)(4)][BF4](2), thin film has been demonstrated. The catalyst is deposited by nebulization of dilute solutions onto a quartz crystal microbalance (QCM) and then exposed to styrene vapor in controlled environments. The use of QCM allows in situ monitoring of catalyst deposition and polymer growth kinetics. The polymerization process appears to involve the entire catalyst film rather than polymerization only at the catalyst film surface. The styrene vapor polymerization occurs rapidly after a short induction time needed for monomer dissolution and catalyst activation. The narrow molecular weight distribution of the produced polymer suggests that the deposited film acts as a single site catalyst. (c) 2005 Wiley Periodicals, Inc.