Surface and bulk composition of amorphous metallic alloys (AMA) has been analyzed by AES and SIMS. Original surface segregation and its variation has been studied in detail under the effect of different treatment techniques. Secondary ion energy distributions were measured for different structural states and primary ions. Data obtained can be used in practical SIMS analysis. Kinetical characteristics of secondary ion emission (SIE) are shown to be useful for surface characterization. Structure-sensitive SIE is changed greatly and irreversibly during transition from the amorphous to the crystalline state.