The nature of interactions of thiophene with six kinds of hydrides (Y) (Y=HF, HCl, H₂O, H₂S, NH₃, PH₃) was investigated using ab initio calculations at MP2/aug-cc-pVDZ theoretical level. In contrast with the previous results on similar furan complexes, only the H-pi type complex was observed for thiophene. Variations in complexes geometry can be accounted for the differences in the electrostatic potential on the aromatic ring. To further study the nature of the intermolecular interactions, a Symmetry-Adapted Perturbation Theory (SAPT) energy decomposition analysis was carried out and the results indicated that the dispersion and electrostatic interactions dominate the thiophene complexes.