The valence electron structures and the properties of ANi5 (A=La, Ca, Y) hydrogen storage alloys were calculated according to the empirical electron theory of solids and molecules (EET). Results show that there exist good correlations among their electron structures and hardness, anti-pulverization abilities together with equilibrium hydrogen pressures at the room temperature. The theoretical results agree with that of experiments and have a theoretical guiding significance to improving the hydrogen storage properties of ANi5 alloys with the element substitution method and exploring versatile hydrogen storage alloys suitable for different situations.