The inner structure of W18O49 mesocrystals was observed by electron microscopy with the help of ultramicrotomy and focused ion beam techniques. The results showed that these mesocrystals contain irregular mesopores formed through partial fusion of self-assembled nanowires, and consequently have long-range structural ordering in one dimension and short-range ordering in the other two dimensions. The W18O 49 mesocrystals exhibit superior performance in gas sensing applications, which is considered to be associated with the presence of more oxygen vacancy sites in the unique mesoporous structure. © 2013 The Royal Society of Chemistry.