Lanthanide ions are extensively utilized in optoelectronic materials, owing to their narrow emission bandwidth, prolonged lifetime, and elevated fluorescence quantum yield. Inorganic non-metallic materials commonly serve as host matrices for lanthanide complexes, posing noteworthy challenges regarding loading quantity and fluorescence performance stability post-loading. In this investigation, an enhanced Stöber method was employed to synthesize mesoporous hollow silica, and diverse forms of SiO2@Eu(TTA)3phen (S@Eu) were successfully prepared. Transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) outcomes revealed the effective binding of silica with Eu(TTA)3phen through both physical adsorption and chemical bonding. This includes the formation of Si-O-C bonds between silica and the ligand, as well as Si-O-Eu bonds between silica and europium ions. Fluorescence tests demonstrated that the mesoporous SiO2@Eu(TTA)3phen(MS@Eu) composite exhibited the highest fluorescence intensity among the three structured silica composites, with a notable enhancement of 46.60% compared to the normal SiO2@Eu(TTA)3phen composite. The Brunauer–Emmett–Teller (BET) analysis indicated that the specific surface area plays a crucial role in influencing the fluorescence intensity of SiO2@Eu(TTA)3phen, whereby the prepared mesoporous hollow silica further elevated the fluorescence intensity by 61.49%. Moreover, SiO2@Eu(TTA)3phen demonstrated 11.11% greater cyclic stability, heightened thermal stability, and enhanced alkaline resistance relative to SiO2@Eu(TTA)3phen.