In recent years, water (R718) as a kind of natural refrigerant—which is environmentally-friendly, safe and cheap—has been reconsidered by scholars. The systems of using water as the refrigerant, such as water vapor compression refrigeration and heat pump systems run at sub-atmospheric pressure. So, the research on water boiling heat transfer at sub-atmospheric pressure has been an important issue. There are many research papers on the evaporation of water, but there is a lack of data on the characteristics at sub-atmospheric pressures, especially lower than 3 kPa (the saturation temperature is 24 °C). In this paper, the experimental research on water boiling heat transfer on a horizontal copper rod surface at 1.8–3.3 kPa is presented. Regression equations of the boiling heat transfer coefficient are obtained based on the experimental data, which are convenient for practical application.