Described is a direct method for the fabrication of resorcinarene nanocapsules by photopolymerization of compounds of formula (I), such as resorcinarene tetraalkene tetrathiol (RTATT), in the absence of any template or preorganization. Further, by varying the polymerization media, a variety of other polymeric architectures like lattices, fibrous networks, and nanoparticles were obtained. The morphology and structure were characterized by transmission electron microscopy, energy dispersive spectroscopy, scanning electron microscopy, dynamic light scattering, infrared and nuclear magnetic resonance spectroscopy. These morphologically distinct resorcinarene polymeric architectures contain residual thiol and ene functional groups offering potential functionalization opportunities.