In this work, recovery performance of a novel sort of form stable phase change materials (FSPCMs) with simultaneously shape memory properties was investigated systematically. The FSPCMs comprising hexadecane as latent heat storage material and olefin block copolymer (OBC) as supporting material were prepared by simple swelling preparation method. This kind of difunctional materials exhibits fantastic shape memory properties with mass fraction of hexadecane reaching 70 wt%, which indicates excellent energy storage ability as well. It is found that the recovery performance under 50% strain is obviously better than that under higher strains for all the specimens investigated, while surprisingly, the composite with 70 wt% hexadecane exhibits better recovery performance than pure OBC as well as the composite with 30 wt% hexadecane at strains of 100 and 200%. The structural change brought by incorporation of hexadecane was explored with in situ two-dimensional X-ray scattering measurements. According to experiment results, we find that the recovery performance is closely correlated to change of long period, indicating the irreversible deformation of the difunctional materials may originate from lamellar fragmentation of OBC, while addition of massive hexadecane is beneficial to restrain lamellar fragmentation and thus improves the recovery performance. We believe this exploration may shed light on comprehending the relationship between structural change and shape memory performance, thus contributing to adjusting the properties of the difunctional materials and expanding their potential applications. (C) 2014 Elsevier B.V. All rights reserved.