NaBH4 was widely regarded as a low-cost hydrogen storage material due to its high-weight hydrogen capacity of approximately 10.8% (mass) and high volumetric hydrogen capacity of around 115 g·L–1. However, it exhibits strong stability and requires temperatures above 500 °C for hydrogen release in practical applications. In this study, two polyhydric alcohols xylitol and erythritol (XE) were prepared as a binary eutectic sugar alcohol through a grinding-melting method. This binary eutectic sugar alcohol was used as a proton-hydrogen carrier to destabilize NaBH4. The 19NaBH4-16XE composite material prepared by ball milling could start releasing hydrogen at 57.5 °C, and the total hydrogen release can reach over 88.8% (4.45% (mass)) of the theoretical capacity. When the 19NaBH4-16XE composite was pressed into solid blocks, the volumetric hydrogen capacity of the block-shaped composite could reach 67.2 g·L–1. By controlling the temperature, the hydrogen desorption capacity of the NaBH4-XE composite material was controllable, which has great potential for achieving solid-state hydrogen production from NaBH4.