The role of three kinds of surfactant (by means of PEG, Tween 80, and SDS) on subcritical water (SCW) hydrolysis of coconut husk towards the reducing sugar production was studied comprehensively. The addition of Tween gave a significant escalation of sugar yield below the cloud point (around 130 °C). The simultaneous hydrophobic and hydrophilic interaction between lignin and SDS drove the highest delignification and solubilization of monomeric sugar during SCW process. On the contrary, adding PEG showed an adverse effect on the subcritical condition. The best scenario of surfactant addition producing higher sugar production was by the addition on SCW instead of enzymatic hydrolysis. The combination of SCW assisted by SDS and enzymatic hydrolysis generated the highest sugar yield and minimized the degradation compound and energy consumption, resulting in favorable fermentable sugar for subsequent biofuel process.