Bio-waste utilization is essential, and pyrolysis is a prominent way for its effective utilization. However, the gradual accumulation of ash compounds in the intermediate products probably affects the thermal conversion characteristics of bio-waste. In the present study, beech wood and disposable chopsticks were selected as bio-waste samples. The effects of typical ash components (Ca-compounds) on volatile formation behavior were investigated during the molten salts thermal treatment of bio-waste. Results demonstrated that about 80% mass of initial bio-waste was gasified into the volatiles at 300 °C. The introduction of Ca-compounds in the molten salts slightly decreased the total yield of gaseous products. More specifically, Ca2+ could improve the generation of CO2 and suppress the generation of other gases (CO, H2, and CH4), and this is accompanied by a reduction in the low heating value (LHV) of the gases. The possible reason is that Ca2+ might act on the -OH bonds, phenyl C-C bond, methoxy bond and carboxylic acid -COOH bonds of the bio-waste to promote CO2 release. In contrast, the introduction of CO32− and OH- tended to relieve the inhibition effect of Ca2+ on the generation of H-containing gases. Meanwhile, the introduction of Ca2+ can promote the conversion of bio-waste into liquid products as well as increase the saturation level of liquid products. Moreover, as a vital form of carbon storage, CO2 was found to be abundant in the pyrolysis gases from molten salts thermal treatment of bio-waste, and the concentration of CO2 was much higher than that of direct-combustion or co-combustion with coal. It’s a promising way for bio-waste energy conversion as well as synchronized CO2 capture by using molten salts thermal treatment, while the introduction of small amounts of Ca-compounds was found to have no significant effect on the change of CO2 concentration.