Mg2Si films, prepared by pulsed laser deposition (PLD), were amorphous, as prepared, and nanocrystalline following annealing. Their micro-structure and electrochemical characteristics were studied by high-resolution transmission electron microscopy (HRTEM) and electrochemical cycling against lithium. HRTEM analysis revealed that some excess Si was present in the films. The more amorphous thinner film exhibited excellent cyclability. However, when the film becomes crystalline, the irreversible capacity loss was more significant during the initial cycling and after ∼50 cycles. Interpretations of the superior stability of the amorphous films are examined.