Upconverting nanocrystals are widely used in the field of trace substance detection, but quantitative analysis with high sensitivity remains challenging. In this paper, we developed a novel optical sensing material for food pigment detection. A series of upconverting nanocrystals Na3GaF6:Ho3+,Yb3+ with a monoclinic phase were synthesized by the coprecipitation method. To modify the nanocrystal surface and limit luminescence quenching, Na3GaF6:Ho3+,Yb3+@SiO2 upconverting materials with a core–shell structure were designed, where the high-intensity upconversion emission was realized by the modulation of the Ho3+/Yb3+ doping ratio and SiO2 shell layer thickness. Simultaneously, based on the fluorescence resonance energy transfer phenomenon, we applied the Na3GaF6:Ho3+,Yb3+@SiO2 upconversion luminescent material to the concentration detection of food pigment (amaranthine red), and the detection mechanism was also analyzed in detail. In addition, this work presents a promising strategy for food pigment detection with high sensitivity and selectivity, which holds significant practical value and effectively safeguards human health.