Hydrophobic nanoparticles (NPs) in water were considered unstable because they lack the repulsive electrostatic interaction and steric effect to prevent aggregation. In this study, porous hydrophobic NPs of two star-shaped giant molecules, POSS-(R)8, were found to be stable in water and able to retain their kinetic stability in a wide range of temperatures, pH values, and ionic strengths. Unlike the solid hydrophobic NPs that aggregate even with the negative zeta potential (ζ) induced by surface-structured hydrogen-bonded (SHB) water, the porous morphology of POSS-(R)8 NPs reduces the entropically driven hydrophobic effect to prevent aggregation. With the porous morphology, the hydrophobic NPs are stable without the hydrophilic or charged surface functional groups and demonstrate good encapsulation capability. The morphological factor of colloids is thus one of the missing pieces in the theory of colloidal stability that extends our understanding of colloidal science.