Metal‐organic frameworks (MOFs) hold great promise as high‐energy anode materials for next‐generation lithium‐ion batteries (LIBs) due to their tunable chemistry, pore structure and abundant reaction sites. However, the pore structure of crystalline MOFs tends to collapse during lithium‐ion insertion and extraction, and hence, their electrochemical performances are rather limited. As a critical breakthrough, a MOF glass anode for LIBs has been developed in the present work. In detail, it is fabricated by melt‐quenching Cobalt‐ZIF‐62 (Co(Im)1.75(bIm)0.25) to glass, and then by combining glass with carbon black and binder. The derived anode exhibits high lithium storage capacity (306 mAh g−1 after 1000 cycles at of 2 A g−1), outstanding cycling stability, and superior rate performance compared with the crystalline Cobalt‐ZIF‐62 and the amorphous one prepared by high‐energy ball‐milling. Importantly, it is found that the Li‐ion storage capacity of the MOF glass anode continuously rises with charge–discharge cycling and even tripled after 1000 cycles. Combined spectroscopic and structural analyses, along with density functional theory calculations, reveal the origin of the cycling‐induced enhancement of the performances of the MOF glass anode, that is, the increased distortion and local breakage of the CoN coordination bonds making the Li‐ion intercalation sites more accessible. A ZIF glass (melt‐quench Co ZIF‐62 glass), for the first time, is evaluated as anode for high performance lithium‐ion batteries. This ZIF glass anode exhibits an unusual capacity enhancement during charge‐discharge cycling. This exceptional phenomenon is related to the unique structure of ZIF glass, e.g., short‐range disorder.