Upon evaporation, ZnO nanorods in a nanofluid droplet undergo rapid and spontaneous chemical and morphological transformation into centimetre-long Zn(OH)2 fibres, via a mechanism very different from that for coffee rings. We show that the detailed nanostructure and micromorphology in the residual thin film depend intricately on the ambient moisture, nanofluid solvent composition and substrate surface chemistry. Upon thermal annealing, these Zn(OH)2 fibres readily undergo further chemical and morphological transformation, forming nanoporous fibres with the pore size tuneable by temperature. Our results point to a simple route for generating a self-assembled 3D structure with ultralong and nanoporous ZnO/Zn(OH)2 fibres/belts, and may also be of interest to the fields of evaporation controlled dynamic self-assembly, non-equilibrium crystallisation, and flow and fingering instabilities in nanofluids.