Drop-on-demand metal jetting is a promising additive manufacturing (AM) technology that is gaining interest due to its capability to directly print complex single and multi-material components at high resolutions. It also has key advantages over other metal AM techniques, such as avoiding powder handling and extensive post-processing. In this method, parts are built via spatially controlled deposition of individual molten droplets onto a substrate. Therefore, the success of the process entirely depends on the behaviour of these single droplets from deposition to solidification including their interactions with the substrate, which is scarcely investigated to date. To fill this research gap, the in-house MetalJet platform was used to investigate the spreading and solidification of metallic micro-droplets at low Weber numbers. This was undertaken onto various substrates using a range of jetting and substrate temperatures through an integrated experimental, analytical, and computational approach. This study reports that increasing the substrate temperature enhanced the diffusion between the droplet and substrate, hence improving the bonding. Moreover, ripples forming on a droplet’s periphery during solidification disappeared at elevated substrate temperatures, resulting in improved inter-droplet bonding. Furthermore, the significant role of the substrate wettability and thermal properties, which control the droplet’s dynamics and solidification behaviour, respectively, is elucidated. This highlights the importance of substrate material selection using this technology. The results presented in this article underpin the optimal process conditions under which the 3D structures produced with this technology can exhibit reliable integrity and consistency. This represents a step forward in the direct metal printing of high resolution functional multi-material components.