A composite liquid crystalline elastomer is designed, combining main‐chain and side‐chain mesogenic polymers in the network, and resulting in micro‐phase separated regions of nematic and smectic ordering in the macroscopically homogeneous elastomer. A range of different fractions of the components is explored, from fully nematic main‐chain system, across to fully smectic side‐chain elastomer. Thermal phase transitions of both phases coexisting in the material are detected by calorimetry, and the nematic/smectic structure investigated by X‐ray scattering. The tensile stress–strain data reveal the key effect of such a multi‐phase composite, where the nematic fraction adds ductility while the smectic fraction increases the modulus and mechanical stiffness. Varying the composition, the authors are able to optimize the mechanical properties of this material type
