A calcium nitrate prompted solvent-free Michael addition reaction of nitroalkenes with malonate esters to synthesize γ-nitro ester compounds by ball-milling method has been developed. The reaction is carried out at a frequency of 20Hz，and takes 30min to complete conversion. Nitroalkenes and their derivatives reacted with malonate esters obtain the target product with the yield of more than 80% , especially when there are two electron-withdrawing groups in the ortho position of the phenyl ring of nitrostyrene, the yield is up to 95%.