This review delves into the forefront of upconversion luminescence (UCL) research, focusing on KY3F10-based compounds, particularly their cubic α-phase. These materials are renowned for their exceptional luminescent properties and structural stability, making them prime candidates for advanced photonic applications. The synthesis methods and structural characteristics of the existing works in the literature are meticulously analyzed alongside the transformative effects of various doping strategies on UCL efficiency. Incorporating rare earth (RE) sensitizer ions such as Yb3+, along with activator ions like Er3+, Ho3+, Nd3+, or Tm3+, researchers have achieved remarkable enhancements in emission intensity and spectral control. Recent and past breakthroughs in understanding the local structure and phase transitions of single-, double-, and triple-RE3+-doped KY3F10 nanocrystals are highlighted, revealing their pivotal role in fine-tuning luminescent properties. Furthermore, the review underscores the untapped potential of lesser-known crystal structures, such as the metastable δ-phase of KY3F10, which offers promising avenues for future exploration. By presenting a comprehensive analysis and proposing innovative research directions, this review aims to inspire continued advancements in the field of upconversion materials, unlocking new potentials in photonic technologies.