White upconversion (UC) luminescent materials have shown incomparable advantages over other light sources in the fields of solid-state lighting, liquid crystal display, and bioimaging, and received extensive attention from researchers. In this work, a series of microcrystals doped with different ion concentrations is synthesized by hydrothermal method, such as NaYF₄: Yb³⁺/Ho³⁺/Tm³⁺ and NaYF₄: Yb³⁺/Ho³⁺/Tm³⁺, and their corresponding micron core-shell (CS) structures are constructed based on epitaxial growth technology. The structure and morphology of the prepared microcrystals are characterised by X-ray diffractometer (XRD) and scanning electron microscope (SEM), showing that the microcrystal has a pure hexagonal-phase crystal structure with a rod-like shape. Under the excitation of 980 nm near-infrared laser, the white UC luminescence characteristics of Ho³⁺/Tm³⁺ and Er³⁺/Tm³⁺ co-doped single-particle NaYF₄ microcrystals are systematically studied by modulating the concentration of the doping ions. The study shows that in Ho³⁺/Tm³⁺ co-doped NaYF₄ microcrystals, white UC luminescence can be easily achieved by modulating the concentration of Yb³⁺ ions, while in the Er³⁺/Tm³⁺ co-doped NaYF₄ microcrystal, the white UC luminescence can be effectively achieved by modulating the concentration of Er³⁺ ions. According to the luminescence characteristics of the microncrystals in different doping systems, the physical mechanism of white light emission regulation is revealed, which is mainly due to the interaction between the doped ions, including cross relaxation (CR) process and energy back transfer (EBT) process. Meanwhile, an effective enhancement of the white UC luminescence on CS microrod is achieved by coating the NaYF₄ inert shell. Therefore, ion doping technique and the construction of CS structure can not only realize the white UC luminescence of microrods, but also provide important experimental reference for further enhancing the luminescence characteristics of microrods, and expand the applications of microcrystals in the fields of display, optoelectronics and anti-counterfeiting.