A novel solvent-relief-self-seeding (SRSS) process was applied to grow bulk polygonal tubular single crystals ofSb
2E
3 (E = S, Se), using SbCl
3 and chalcogen elements E (E = S, Se) as the raw materials at 180
C for 7 daysin ethanol solution. The products were characterized by various techniques, including X-ray powder diffraction(XRD), scanning electronic microscope (SEM), transmission electronic microscope (TEM), electronic diffraction(ED), and X-ray photoelectron spectra (XPS). The calculated electrical resistivities of the tubular single crystals inthe range 20-320 K were of the order of 10
5-10
6 cm for Sb
2S
3 and 10
3-10
4 cm for Sb
2Se
3, respectively.The studies of the optical properties revealed that the materials formed had a band gap of 1.72 eV for Sb
2S
3 and1.82 eV for Sb
2Se
3, respectively. The optimal reaction conditions for the growth of bulk tubular single crystals werethat the temperature was not lower than 180
C and the reaction time was not shorter than 7 days. The possiblegrowth mechanism of tubular crystals was also discussed.