The emission characteristic of VOCs from biomass molding fuel combustion was studied. VOCs emission factor and the components of flue gas after combustion from four kinds of biomass shaped fuel, i.e., corn straw, wheat straw, cotton stalk and wood, were analyzed on the biomass combustion experimental platform using the sample collection-GC/MS method. The results showed that the VOCs emission factors of four kinds of biomass molding fuel were 0.447, 1.111, 0.601 and 0.104 g/kg, respectively. The VOCs emission factors of biomass molding fuel were only 50% of the powder burning straw. The main types of VOCs from wood molding fuel combustion emissions were benzene series, halogenated hydrocarbon and ketones. The main kinds of VOCs from straw molding fuel combustion emissions were halogenated hydrocarbon, ketone and benzene series. The benzene content emission factor of total straw produced by lignocellulosic biomass combustion was nearly five times higher than that of VOCs emission proportion coefficient. Biomass molding fuel combustion emitted the most of hydrocarbon and ketone with contents of 49.8% and 36.1%, respectively. The ozone generating potential (O3) of total VOCs emissions from four kinds of biomass molding fuel combustion were 4.792, 25.737, 9.598 and 4.502 g/kg, respectively. The compounds with higher ozone generating potential were benzene, ketone, olefins and halogenated hydrocarbon. The results will provide reference for industry standards built of VOCs emissions from biomass molding fuel combustion.