The surface status, structure relaxation and crystallization process of Fe35Ni15B26 nanometer metglas produced by chemical reduction method were investigated by using X-ray photoelectron spectroscopy and M?ssbauer spectroscopy. The experimental results indicated that it is rich in nickel and lack in iron on the oxidized particle surface compared with the bulk composition of the particles. The change of hyperfinc field distributions during structure relaxation is correlated with the variance of short range order. The crystallization product is different from that of traditional amorphous ribbon with the similar composition because of the heterogeneous distribution of elements in particles.