This study reports the design of a stimulus-responsive fabric incorporating a combination of microcapsules, containing polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) sodium salt (PSS), formed via a layer-by-layer (LBL) approach. The use of PAH and PSS ensured that the microcapsule structure was robust and pH-sensitive. SEM and TEM studies showed that the composite microcapsule (PAH/PSS)_nPAH had a spherical morphology with a hollow structure. FTIR demonstrated the presence of PAH and PSS, confirming the composition of the microcapsule shell. DSC showed that the microcapsules were thermally stable. The size of the microcapsules ranged from 4 μm to 6 μm. The hollow microcapsules can be used as a carrier for loading and releasing chemicals under different pH conditions. The release rate of Rhodamine-B from (PAH/PSS)_nPAH microcapsules was higher at pH 5.8 than that at 7.4, confirming the pH sensitivity. The hollow structure of (PAH/PSS)_nPAH microcapsules is expected to act as a carrier and medium to introduce functional chemicals into the fabric with long-lasting property and pH stimulus responsivity. Furthermore, a positively charged compound with ethylene oxide groups was added during the coating process as a crosslinker binding (PAH/PSS)₂PAH for the microcapsules with the cotton fabric more efficiently. Using this method, numerous substances, e.g., drugs, dyes, natural herbs, or perfumes, could be stored into the LBL microcapsules for a relatively long time, constantly releasing them from the coated textiles. Since LBL microcapsules were easy to combine with fabrics, this study provided a feasible approach for the preparation of functional stimulus-responsive textiles.