The geometric configuration and electronic structure of NaBen (n=1—12) clusters have been studied by using density functional theory (DFT).The results show that the atomic structures of NaBen (n=1—12) clusters are significantly different from the host geometries; the nearest inter-atomic distances of Na-Be and the energy gaps (HOMO-LUMO) oscillate with increasing size. It is found that at size n=4, 6 and 9, the clusters are more stable than neighboring ones, especially the NaBe4 cluster. Also, the evolution with increasing size for the electronic properties of NaBen (n=1—12) clusters are discussed.