This study consists of the synthesis, characterization, and analysis of photoluminescence (PL) spectra for Li 2 O−HfO 2 −SiO 2 −Yb 2 O 3 glass ceramics sensitized with small amounts of Au 2 O 3 . Using the results of XRD and X-ray photoelectron spectroscopy (XPS) studies indicated a progressive reduction of Au 3+ ions into Au 0 metallic particles (MPs) with increase of Au 2 O 3 content. Investigations into the infrared spectra highlighted a growing concentration of induced defects in the samples due to the increased proportion of Au 0 MPs. Optical absorption (OA) spectra exhibited a distinct band attributed to the 2 F 7/2 → 2 F 5/2 transition of Yb 3+ within wavelength range of 800–980 nm. Furthermore, a wide absorption band linked to the surface plasmon resonance (SPR) of Au 0 MPs was identified in the visible region. PL spectra, recorded at λ exc  = 450 nm, revealed a band between 980 to 1025 nm, associated with the 2 F 5/2 → 2 F 7/2 transition of Yb 3+ ions. Another emission band was observed due to the sp → d transition of Au 0 MPs within the visible region. Observed enhanced PL emission from Yb 3+ ions in the NIR range was ascribed to the energy transfer from Au 0 MPs to Yb 3+ ions. Ultimately, it was deduced that Au 0 MPs played a pivotal role in enhancing the PL output of Yb 3+ ions in the Li 2 O−HfO 2 −SiO 2 glass ceramic. Thus, glass ceramics incorporating an optimal concentration of Au 2 O 3 hold significant potential as materials for NIR lasers.