Phenol-formaldehyde resins (PhFR) with reactive methacrylate fragments or labile peroxy bonds in the side branches used as a polymeric component of bitumen-polymeric mixtures have been investigated. Taking into account that PhFR with peroxy fragments based on epoxy resin does not described in literature, its synthesis procedure has been developed. The kinetic regularities of the reaction between peroxy derivative of epoxy resin (PDER) and phenol group of PhFR were studied taking the reaction of PDER with phenol as an example. The structure of PhFR with peroxy groups (PhFRP) has been confirmed by IR-studies. Bitumenpolymeric mixtures with PhFRP or PhFR with unsaturated fragments (PhFRU) in the amount of 1, 3, 5 or 7 mass parts per 100 g of petroleum bitumen were examined at 443, 463 or 483 K for 0.5, 1.0 or 2.0 h. The composition of bitumn-polymeric mixtures has been determined using the group analysis.