The present invention relates to an extreme low formaldehyde emission UF resin with a novel structure, and a process for its preparation. This UF resin is produced from formaldehyde, urea, a long chain multi-aldehyde prepolymer, and some modifiers. Its process follows three steps: weak caustic, weak acid and weak caustic. By using this prepolymer, the modified UF resin has stable alkyl ether structure, and the residual aldehyde groups on the UF polymer chain could accelerate cross-linking instead of dissociative formaldehyde. The UF resin made from this invention has extreme low dissociative formaldehyde and simple technology. The boards produced from this resin have good physical performance and water resistance. Moreover, the formaldehyde emission of the boards is extreme low, achieving Japan F⋆⋆⋆⋆ grade, the average emission value ≦0.3 mg/L.