A series of ternary lanthanide β-diketonate derivatives covalently bonded to xerogels (named as Ln-DP-xerogel, Ln = Sm, Yb, Nd, Er, Pr, Ho) by doubly functionalized alkoxysilane (dbm-Si) was synthesized in situ via a sol-gel process. The properties of these xerogel materials were investigated by Fourier-transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and fluorescence spectroscopy. The data and analyses suggest that the lanthanide derivatives have been covalently grafted to the corresponding xerogels successfully. Of importance here is that, after excitation with visible light (400-410 nm), the xerogels all show characteristic visible (Sm(3+)) as well as near-infrared (NIR; Sm(3+), Yb(3+), Nd(3+), Er(3+), Pr(3+), Ho(3+)) luminescence of the corresponding Ln(3+) ions, which is attributed to the energy transfer from the ligands to the Ln(3+) ions via an antenna effect. Exciting with visible light is advantageous over UV excitation. Furthermore, to the best of our knowledge, it is the first observation of NIR luminescence with visible light excitation from xerogels covalently bonded with the Sm(3+), Pr(3+), and Ho(3+) derivatives. Compared to lanthanide complexes (Ln = Er, Nd, Yb) functionalized periodic mesoporous organosilica (PMO) materials that exhibit similar optical properties reported in our previous work, the Ln-DP-xerogel (Ln = Sm, Yb, Nd, Er, Pr, Ho) in this case offer advantages in terms of ease of synthesis and handling and potentially low cost for emerging technological applications. Development of near-infrared luminescence of the lanthanide materials with visible light excitation is of strong interest to emerging applications such as chemosensors, laser systems, and optical amplifiers.