As a promising candidate for expanding the capacity of drug loading in silica nanoplatforms, hollow mesoporous silica nanoparticles (HMSNs) are gaining increasing attention. In this study, porous nanosilica (PNS) and HMSNs were prepared by the sol-gel method and template assisted method, then further used for Rhodamine (RhB) loading. To characterize the as-synthesized nanocarriers, a number of techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen absorption-desorption isotherms, dynamic light scattering (DLS), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR) were employed. The size of HMSN nanoparticles in aqueous solution averaged 134.0 ± 0.3 nm, which could be adjusted by minor changes during synthesis, whereas that of PNS nanoparticles was 63.4 ± 0.6 nm. In addition, the encapsulation of RhB into HMSN nanoparticles to form RhB-loaded nanocarriers (RhB/HMSN) was successful, achieving high loading efficiency (51.67% ± 0.11%). This was significantly higher than that of RhB-loaded PNS (RhB/PNS) (12.24% ± 0.24%). Similarly, RhB/HMSN also possessed a higher RhB loading content (10.44% ± 0.02%) compared to RhB/PNS (2.90% ± 0.05%). From those results, it is suggested that prepared HMSN nanocarriers may act as high-capacity carriers in drug delivery applications.