Commonly used dicumyl peroxide (DCP) in combination with coagent, triallyl cyanurate (TAC), as a crosslinking agent is well acceptable for dynamically vulcanized rubber phase of thermoplastic vulcanizates (TPVs). However, it generally produces volatile decomposition products, which cause a typical unpleasant smell and a blooming phenomenon. In this work, influence of two types of multifunctional peroxides: 2,4-diallyloxy-6-tert-butylperoxy-1,3,5-triazine (DTBT) and 1-(2-tert-butylperoxyisopropyl)-3-isopropenyl benzene (TBIB), on properties of TPVs based on epoxidized natural rubber (ENR)/ polypropylene (PP) blends were investigated. The conventional peroxide/coagent combinations, i.e., DCP/TAC and tert-butyl cumyl peroxide (TBCP)/alpha-methyl styrene (alpha-MeS) were also used to prepare the TPVs for a comparison purpose. The TPVs with multifunctional peroxide, DTBT, provided good mechanical properties and phase morphology of small dispersed vulcanized rubber domains in the PP matrix which were comparable with the DCP/TAC cured TPVs. However, the TPVs with TBIB/alpha-MeS and TBCP/alpha-MeS showed comparatively low values of the tensile properties as well as rather large phase morphology. The results were interpreted by three main factors: the kinetic aspects of the various peroxides, solubility parameters of respective peroxide/coagent combinations in the ENR and PP phases, and the tendency to form unpleasantly smelling byproducts. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 111: 819-825, 2009