The invention discloses water-soluble NaYF4:Yb, Er@NaGdF4 core-shell nanocrystalline as well as a preparation method and applications of the water-soluble NaYF4:Yb, Er@NaGdF4 core-shell nanocrystalline in nuclear magnetic resonance. The preparation method of the water-soluble NaYF4:Yb, Er@NaGdF4 core-shell nanocrystalline is characterized by comprising the following steps: under the condition with excessive fluorinated ammonia and sodium hydroxide, rapidly injecting a compound formed by mixing ytterbium oleate, erbium oleate and yttrium oleate at a certain ratio at high temperature, thus preparing 10-sub-nanometer NaYF4: Yb, Er nanocrystalline, further rapidly injecting a certain amount of gadolinium oleate compound at high temperature, thus preparing oil-soluble NaYF4:Yb, Er@NaGdF4 core-shell nanocrystalline with a thin shell layer, and carrying out water-soluble surface modification on the oil-soluble NaYF4:Yb, Er@NaGdF4 core-shell nanocrystalline by adopting polyethylene glycol-polyacrylic acid (PEG-PAA), thus obtaining the target product. The preparation method of the water-soluble NaYF4:Yb, Er@NaGdF4 core-shell nanocrystalline is simple, the obtained product as a T1 nuclear-magnetic contrast agent has very high longitudinal Moore relaxation rate r1, wherein r1 is 15-25 mM<-1>S<-1>, and thus the product has a great clinical application value.