Abstract: Layer-by-Layer (LbL) assembly technique to prepare hollow microcapsules has broad prospects in textile applications. Poly(styrene sulfonate) (PSS) doped (PSS) calcium carbonate (CaCO3) particles was employed as a template, poly(allylamine hydrochloride) (PAH) and PSS were alternately deposited on the template. The influence of PSS content on the template size and morphology and the loading efficiency of microcapsules were investigated. SEM and TEM were used to observe the morphology and hollow structure of microcapsules; thermal gravimetric analysis (TGA) and UV-vis spectrophotometer were used to characterize the nature of microcapsules. The results showed that the PSS-doped CaCO3 particles are all spherical and the higher concentration of PSS leads to smaller CaCO3 particles size, the PSS amount in CaCO3 particles is 2.73% ~ 5.12%, PSS trapped inside the microcapsules has no effect on its morphology and structure, vacuum drying is better than hot air drying, the resulting microcapsules have a deposition effect for RhB.