Tetrapod-shaped CdSe nanocrystals have been successfully synthesized in high yields using a simple method of controlling the protonic acidity of the reaction system. A possible growth mechanism is discussed on the basis of the surface modification of H+ present. The crystal structure of CdSe tetrapods is determined by high-resolution transmission electron microscopy analysis to have a zinc blende core at the center with four wurtzite arms growing out from the core along four [111] directions. The electronic structure of CdSe tetrapods is studied theoretically in comparison with that of spherical dots.