Photoactuating composites based on the linear triblock copolymer polystyrene-b-polyisoprene-b-polystyrene (SIS) were prepared by incorporation of polystyrene-modified multiwalled carbon nanotubes (MWCNT-PS). Modification of MWCNT was performed by surface-initiated atom transfer radical polymerization (SI ATRP) of styrene. The presence of the polystyrene chains on the MWCNT surface facilitated their dispersion in the SIS matrix. Improved interactions of the modified MWCNT-PS compared to neat MWCNT were confirmed by dynamic mechanical analysis. The activation energy of glass transition of the polystyrene phase in the MWCNT-PS/SIS composite increased significantly compared to the neat SIS matrix, while the incorporation of neat MWCNT to the SIS matrix disturbed the physical cross-linking of the SIS and degraded its elastic properties. The photo-actuation ability of the MWCNT-PS/SIS composite was proved using atomic force microscopy.