A new thiophene-echinoynethiophene A (11), four new natural products, namely 5,5"-dichloro-alpha-terthiophene (1), 5-chloro-alpha-terthiophene (2), 5-acetyl alpha-terthiophene (3) and 5-carboxyl bithiophene (12), together with seven known thiophenes were isolated and purified from ethanol extract of roots of Echinops grijisii Hance. Their structures were identified on the basis of spectral data.