Single-crystalline CrSi2 nanostructures with a unique hexagonal nanoweb morphology have been successfully synthesized for the first time. These nanowebs span 150-200 nm and are composed of <11<(2)over bar>0> nanowire segments with a thickness of 10-30 nm. It is proposed that surface charges on the (10 (1) over bar0) sidewalls and the minimization of electrostatic energy induce the nanoweb formation. Calculations of the electrostatic energies were used to predict the transitions between different modes of bending, which agreed well with the experimental observations.