Abstract: During the curing process of double emulsions for fabricating poly(a-methylstyrene) (PAMS) capsules by microencapsulation technology, the match of density between the water in oil compound droplet and the outer water phase is vital to the sphericity of PAMS capsules. To investigate the effects of density mismatch on the sphericity of the resulting PAMS capsules, the densities of compound droplets with different inner diameters and polymer oil layer thicknesses were calculated theoretically and measured experimentally during the curing process. Also, the polymer concentrations of the oil phase in the compound droplets during the curing process were further studied. The results show that, the density mismatch between the compound droplets and the outer water phase can be quantitatively controlled by adjusting the compositions of the outer water phase. The curing stage with the polymer concentration of the oil phase increasing from 20% to 60% is the key phase of the curing process. When the density mismatch between the compound droplets and the outer water phase lowering from 0.004 95 g/cm3 to 0.000 02 g/cm3, the number percentage of PAMS capsules with out of round(OOR） value less than 10 m in batches can be increased from 14.3% to 93.3%. Thus for the compound droplets with different inner diameters and polymer oil layer thicknesses, the sphericity of the resulting PAMS capsules can be significantly improved, through reducing the density mismatch between the compound droplets and the outer water phase in the key phase of the curing process.