This review provides an overview of the current state‐of‐the‐art of the emerging field of flexible multifunctional sensors for wearable and robotic applications. In these application sectors, there is a demand for high sensitivity, accuracy, reproducibility, mechanical flexibility, and low cost. The ability to empower robots and future electronic skin (e‐skin) with high resolution, high sensitivity, and rapid response sensing capabilities is of interest to a broad range of applications including wearable healthcare devices, biomedical prosthesis, and human–machine interacting robots such as service robots for the elderly and electronic skin to provide a range of diagnostic and monitoring capabilities. A range of sensory mechanisms is examined including piezoelectric, pyroelectric, piezoresistive, and there is particular emphasis on hybrid sensors that provide multifunctional sensing capability. As an alternative to the physical sensors described above, optical sensors have the potential to be used as a robot or e‐skin; this includes sensory color changes using photonic crystals, liquid crystals, and mechanochromic effects. Potential future areas of research are discussed and the challenge for these exciting materials is to enhance their integration into wearables and robotic applications.

Liquid crystals are 2D patterned with nonpolarized light by a new dye-free photoalignment method.

Tunable photonic crystals exhibiting optical properties that respond reversibly to external stimuli have been developed using liquid crystal networks (LCNs) and liquid crystal elastomers (LCEs).

Controlled and uniform molecular alignment can provide and enhance functionality in polymer films. We first report that masked photopolymerization with non-polarized light enables direct and precise control of molecular alignment without using a conventional molecular alignment layer. The photopolymerization of a mixture composed of an optically anisotropic acrylate monomer and an isotropic dimethacrylate crosslinker induces either unidirectional or complex molecular alignment, depending upon the shape of the photomask. Such molecular alignments are successfully achieved by shear stress arising from molecular diffusion, even when the photopolymerization is carried out at isotropic temperatures of both the monomer mixture and the obtained polymers.