Optical multisensor systems are easy-to-use and inexpensive analytical devices. In this work, we propose an optical multisensor system based on the luminescence of Nd(III) and Yb(III) complexes in the near-infrared (NIR) spectral region. The observed emission bands play the role of secondary light sources for further analysis of milk—for the determination of fat content and for the recognition of adulteration. The samples for analysis were prepared by putting a drop of milk upon a thin glass covering the powdered mixture of lanthanide complexes, which were excited by a light-emitting diode (LED) in the ultraviolet region (the maximum intensity at 365 nm). The diffuse-reflectance spectra of samples were acquired in the short-wave NIR range 750–1100 nm using a portable NIR spectrometer. The developed optical system was tested using two sets of milk samples with varying concentration levels of fat and added urea. The obtained spectral data were analyzed using a number of multivariate prediction and classification methods of chemometrics and the results were statistically compared. The regression and classification model performances achieved in this proof-of-concept study illustrate the feasibility of the optical multisensor analysis based on luminescent light sources in the short-wave NIR range, in particular, for their application in the dairy.