Low-cost poly(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have been widely used as hole-transporting materials (HTMs) in p-i-n perovskite solar cells (PSCs). However, reports on the use of PEDOT-based HTMs in regular PSCs have been rather limited up till now due to the low solubility of PEDOT in organic solvents. In this work, we report three PEDOT derivatives, namely, PEDOT-C6 (P6), PEDOT-C10 (P10), and PEDOT-C14 (P14), with a simple synthetic process by tailoring the length of the alkyl side-chains, and apply them as dopant-free HTMs in mesoscopic n-i-p structured PSCs. It is revealed that the alkyl side-chain length has a significant impact on the film morphology, hole transport capability, and thus the overall solar cell performance. The devices with P10 afford a champion PCE of 16.2% at one sun illumination (100 mW cm(-2), AM 1.5G), which is significantly higher compared to those based on P6 (12.1%) and P14 (14.8%) under identical conditions. This has been the highest PCE reported so far for dopant-free PEDOT-based HTMs in conventional PSCs. The greatly enhanced photovoltaic performance observed for the P10-based devices is mainly attributed to the superior film formation property and hole transport capability of P10. Furthermore, the devices utilizing P10 also show excellent ambient stability, retaining 75% of their initial performance at a relative humidity (RH) of 80% after 120 h due to the high moisture resistivity of the HTM. The present work provides a new avenue for further developing low-cost, efficient, and stable HTMs in PSCs in the future.