The ESR spectrum of Ag-5CB (C5H11-C6H4-C6H4-CN) and Ag-5Py, (C5H11-C5H3N-C6H4-CN) co-condensate film at 90 K showed two doublet lines due to silver atoms included in pi-complexes with cyanobiphenyls and wide anisotropic singlet line with g-factor equal to 2.0030, that could be referred to small silver clusters. It was found the integral intensity of doublet lines decreased during the annealing of samples in temperature range 80-200 K due to thermal decomposition of Ag-5CB complex followed by the aggregation of silver atoms.