Three small molecule organic compounds based on conjugated acetylene-linked methoxy triphenylamine terminal groups with different substituted thiophene cores were synthesized and firstly applied as hole-transporting materials (HTMs). The electron-deficient acetylene linkers can tune the energy levels of frontier molecular orbitals. The physical property measurements show that the HTMs (CJ-05,CJ-06,andCJ-07) possess good stability, hydrophobicity, and film-forming ability. Further, the HTMs were applied in the MAPbI3-based perovskite solar cells (PSCs), and the best power conversion efficiency (PCE) of 6.04%, 6.77%, and 6.48% was achieved, respectively, which implies that they exhibit great potential in photovoltaic applications.