The power-conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have increased rapidly from about 4% to 22% during the past few years. One of the major challenges for further improvement of the efficiency of PSCs is the lack of sufficiently good hole transport materials (HTMs) to efficiently scavenge the photogenerated holes and aid the transport of the holes to the counter-electrode in the PSCs. In this study, we tailor-made two low-cost spiro[fluorene-9,9'-xanthene] (SFX)-based 3D oligomers, termed X54 and X55, by using a one-pot synthesis approach for PSCs. One of the HTMs, X55, gives a much deeper HOMO level and a higher hole mobility and conductivity than the state-of-theart HTM, Spiro-OMeTAD. PSC devices based on X55 as the HTM show a very impressive PCE of 20.8% under 100mW.cm(-2) AM1.5G solar illumination, which is much higher than the PCE of the reference devices based on Spiro-OMeTAD (18.8%) and X54 (13.6%) under the same conditions.