Surface　optimization　of　tribomaterial　is　an　effective　approach　for　enhancing　the　output　performance　of　triboelectric　nanogenerators　(TENGs).　Developing　advanced　surface　structures　and　their　mass　fabrication　method　is　the　essential　technology　component　of　TENG-based　electronics.　Herein,　a　facile,　scalable　synthesis　of　hierarchical　structure　polydimethylsiloxane　(HS-PDMS)　films　with　micro-/nanosurface　morphology　and　their　application　in　TENGS　are　demonstrated.　The　micromorphology　of　the　PDMS　surface　with　random　microcraters　is　achieved　using　water　droplet-based　microtemplates　and　their　rapid　evaporation　approach.　Simultaneously,　the　nanomorphology　on　the　microcrater　surface　with　nanoripples　is　automatically　formed　under　the　action　of　surface　tension　of　the　PDMS　film.　The　effect　of　water　droplet　mass　fraction　and　the　rate　of　heating,　which　play　key　roles　in　the　surface　morphology　and　the　device＇s　electrical　output　control,　are　investigated.　This　fabrication　method　of　HS-PDMS　is　simple　and　scalable,　providing　a　promising　solution　of　developing　tribomaterial　for　practical　TENG-based　electronic　devices.　©　2021　Wiley-VCH　GmbH