Globular microstructures comprising a liquid core and a solid shell that envelops the core comprising polymeric micro- or nanofibres, preferably obtained by electrospinning, comprising a hydrophobic polymer or a mixture of hydrophobic polymer with polymers derived from cellulose or with polyacrylates; the microstructures may have a further coating of nanoparticles or polymeric coating. The microstructures have applications similar to those of "liquid marbles" with improved mechanical properties.