Levoglucosan (LG) obtained from lignocellulosic biomass exhibits great potential as a specific tracer for biomass burning aerosols and as a raw material for synthesizing stereoregular polysaccharides. One potentially viable source of LG is pyroligneous acid (PA). This study investigated the effects of heating temperature on the extraction capability and the chemical composition of distillate and residual fractions. The results demonstrated that vacuum distillation extracted the acids, alcohols, ketones, aldehydes, and other organic matter. When the heating temperature was above 80 °C, the moisture content of the residual fraction was unchanged. The chemical composition of residual fraction was analyzed by gas chromatography-mass spectrometry (GC-MS). The analysis showed that the relative content of the LG, as obtained from the 90 °C distillation temperature, was 75.6%. Thus, it can be used as raw material for subsequent purification.