Highly‐crystalline Gd‐based fluoride upconversion (UC) nanocrystals, including orthorhombic‐phase GdF3:Yb/Er nanoplates (NPLs), hexagonal‐phase NaGdF4:Yb/Er NPLs, monoclinic‐phase K3GdF6:Yb/Er nanoribbons (NRs), and orthorhombic‐phase KGdF4:Yb/Er NRs are controllably synthesized through a simple yet robust method, with all of the products exhibiting strong UC luminescence. Notably, the obtained K3GdF6:Yb/Er NRs have an exceptional quantum yield as high as 0.84% at a low excitation laser power (0.30 W cm−2, 975 nm), as well as long single‐particle UC lifetimes (τ) for green (τ = 0.70 ms) and red (τ = 1.10 ms) emissions. The enhanced luminescence is attributed to the “multiple luminescent center effect,” which is verified via the laser‐selective excitation spectra of deliberately introduced Eu3+ dopants. This method can be extended to the preparation of a number of other nanocrystals, and the UC nanocrystals featuring high luminescence efficiencies can be further tailored for biomedical applications.