PdO‐decorated SnO2 nanocomposites with open porous hierarchical architectures are fabricated through a facile biotemplating sol–gel technique. The sol–gel soakage process is carried out by immersing the templates butterfly wings in Sn‐ and Pd‐ impregnants successively to generate a uniform colloid layer. PdO and SnO2 nanocrystallites come into being with subsequent calcination treatment, and PdO‐decorated SnO2 nanocomposites further construct the parallel main ridges with connective pillars and vertical struts, finally present a 3‐D open porous hierarchical architecture. Benefiting from unique ingredients and structure hierarchy, the nanocomposites give enhanced acetone‐sensing performance of high sensitivity and rapid response/recovery rate