A large fraction of secondary aerosol particles are liquid−liquid phase-separated with an organic shell and an inorganic core. This has the potential to regulate the hygroscopicity of such particles, with significant implications for their optical properties, reactivity, and lifetime. However, it is unclear how this phase separation affects the hygroscopic growth of the particles. Here, we showed a large variation in hygroscopic growth (e.g., 1.14−1.32 under a relative humidity (RH) of 90%) of particles from the forest and urban atmosphere, which had different average core−shell ratios. For this reason, a controlled laboratory experiment further quantifies the impact of the organic shell on particle growth with different RH values. Laboratory experiments demonstrated that (NH 4 ) 2 SO 4 particles with thicker secondary organic shells have a lower growth factor at an RH below 94%. Organic shells started to deliquesce first (RH > 50%) and the phase changes of sulfate cores from solid to liquid took place at an RH higher than 80% as deliquescence relative humidity of pure (NH 4 ) 2 SO 4 . Our study provides the first direct evidence on an individual particle basis that hygroscopic growth behavior of phase-separated particles is dependent on the thickness of organic shells, highlighting the importance of organic coating in water uptake and possible heterogeneous reactions of the phase-separated particles.