Dewetting of polymer thin films has been extensively studied in the past two decades as an approach to produce patterned surfaces. Here we report a novel phenomenon where dewetted polymer droplets spontaneously align on a substrate, and the alignment extends over a large scale (millimeters). The patterns are formed by dewetting a bilayer system formed by poly(4-vinylpyridine) (P4VP) thin film (80 nm) on a polystyrene (PS) thin film (100 nm) prepared by spin-coating. We investigated the mechanism of the spontaneous droplet alignment and concluded that the final aligned pattern results from series of aligned defects on the P4VP, which are formed during spin-coating. We identified experimental parameters that control the appearance and the order of the resulting aligned droplets.