In this report, we present a new method for generating a high-density (2D) droplet array using double-layered polydimethylsiloxane (PDMS) templates containing honeycomb microwells. Without external flow control, a droplet-on-template (DOT) was created by utilizing capillary forces associated with the interfacial tension between the aqueous and oil phases. The DOT process involved three simple steps: (1) vacuum-assisted filling of microwells; (2) excess water removal; and (3) covering the droplet array with oil. To demonstrate the concept of the DOT, we generated spherical water droplets 147, 191, 238, 326 and 405 μm in diameter from corresponding microwells with lengths of 200, 300, 400, 600 and 800 μm, respectively and a height of 76 μm (up to ~10,000 droplets on a template 25 × 25 mm). Two important factors, including the aspect ratio (height-to-length ratio) of the microwell and the interfacial tension of the two phases, were investigated to understand how those factors affect the shape of the droplets (‘sphere’ or ‘dome’). All the droplets were spherical up to an aspect ratio of 0.55. The droplets were dome-shaped for aspect ratios above 0.82. For a 1 mM sodium dodecyl sulfate (SDS) solution, the use of mineral oil (which had the highest interfacial tension studied) produced spherical droplets, but dome-shaped droplets were produced by corn oil and oleic acid.