Deionized water is replacing fluorinated liquids as the preferred choice for two-phase immersion cooling in data centers. Yet, insufficient bubble removal capability at low saturated pressure is a key challenge hindering the widespread application. To solve this issue, this study employs non-ionic surfactant (Tween 20) and asymmetric structures (expanding microchannel) to enhance the boiling performances of deionized water under sub-atmospheric pressure. The research examines the effects of pressure (8.8~38.5 kPa), surfactant concentration (0.1~0.5 mL/L), and heat flux density (10~180 W/cm2) on the boiling heat transfer characteristics and analyzes the mechanism of unusual temperature oscillations induced by surfactants. It was found that the trade-off between the sub-atmospheric pressure, surface tension coefficient, and reduced static contact angle results in pronounced intermittent boiling on the heated surface. Even with the addition of surfactants, the improvement in heat transfer requires demanding conditions. Boiling enhancement throughout all heat flux conditions was achieved when the surfactant concentration was higher than 0.2 mL/L for the expanding microchanneled surface. The heat transfer coefficient reached 6.89 W·cm−2·K−1 under 8.8 kPa, which was 45% higher than without the surfactant. Under the same heat flux and sub-atmospheric pressure, as the concentration increased from 0.1 to 0.5 mL/L, the amplitudes of temperature fluctuation of the plane surface and expanding microchanneled surface decreased from 10 K to 2 K and 18 K to 1 K, respectively. The onset of nucleate boiling and wall superheat of the expanding microchanneled surface gradually decreased with the increase in surfactant concentration, where the onset of nucleate boiling decreased by 10.54 K. When the heat flux is 160 W/cm2, the wall superheat is reduced by 12.8 K.