Surfactant aids boiling enhancement, but the related mechanism is not yet comprehensively understood. For mechanism investigation on surfactant molecule, most of existing studies focused on its hydrophobic part, while research on hydrophilic part is scarce. In this paper, a group of non-ionic Triton surfactants with same functional group but different hydrophilic chain lengths were experimentally tested for pool boiling on flat copper. At critical micelle concentration (CMC), long-chain Tx-405 exhibited higher heat transfer coefficient (97.4 kW/(m2·K)) than Tx-100 (77.1 kW/(m2·K)) and Tx-114 (77.4 kW/(m2·K)). Long-term test indicated a gradually deteriorating trend of heat transfer performance from days on. Solution properties and bubble dynamics were measured. At low concentration, surfactant with shorter hydrophilic chain has better heat transfer performance due to greater surface tension reduction. The increase of hydrophilic chain length improves water affinity of surfactant and thus leads to higher CMC. If there is no restriction for surfactant concentration, a longer hydrophilic chain is favorable for higher heat transfer coefficient at CMC. The results in this paper provide insights for mechanism investigation on surfactant, promote further design of new surfactant, and contribute to the prediction of heat transfer enhancement effect.