The cured network conformations and structural relaxation behaviours of the diglycidyl ether of bisphenol A (DGEBA)-methylhexahydrophthalic anhydride (MHHPA) modified with phenylmethylsiloxane-modified epoxy (PMSE) at different aging temperatures were studied using dynamic mechanical analysis (DMA) and positron annihilation lifetime spectroscopy (PALS). The DMA results revealed that the cured PMSE network can insert into the cured DGEBA network to form interpenetrating polymer networks (IPNs). The structural relaxation behaviours of DGEBA-PMSE-0.4 produced using DGEBA, PMSE, and MHHPA at a ratio of 0.6:0.4:1 by equivalent weight were studied using PALS at 150 degrees C and 55 degrees C. The aging-induced free volume relaxation parameters of DGEBA-PMSE-0.4 at 150 degrees C and 55 degrees C were investigated using the double additive exponential model and the Kohlrausch-Williams-Watts exponential model. For double additive exponential model, only one relaxation time (zeta) of 584.5 h was found at 150 degrees C; By contrast, there were two separate relaxation times of 37.4 h (zeta(1)) and 753.6 h (zeta(2)) at 55 degrees C. The zeta(1) of the IPNs hybrid can be attributed to the network relaxation of PMSE, and the zeta(2) can be attributed to the network relaxation of DGEBA at 55 degrees C. The results suggested the double additive exponential model can effectively predict DGEBA-PMSE hybrid relaxation behaviours. (C) 2015 Elsevier B.V. All rights reserved.