Great research efforts to investigate the glass-forming ability (GFA) in alloys have been made, leading to an observation that a pinpoint composition produces the best glass-forming characteristics. The reason for this observation is still unknown, limiting the development of bulk metallic glasses (MGs) with a relatively large size. In this work, systematic experimental measurements coupled with calculations were performed to address this issue using the NiNb binary alloy system. It is found that the atomic-level packing efficiency and the clusters-level regularity parameters strongly contribute to their GFA. In particular, the best glass former found in a pinpoint composition possesses the local maximum of the atomic-packing efficiency and the highest degree of the cluster regularity. This work provides an understanding of GFA from atomic and cluster levels and will shed light on the development of more MGs with relatively large critical casting sizes.