The structural properties of fluorine containing polymer compounds make them highly attractive materials for hydro-oleophobic applications. However, most of these exhibit low surface energy and poor adhesion on the substrates. In the present investigation, crack free, smooth and uniform thin films of poly[4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole]-co-tetrafluoroethylene (TFD-co-TFE) with good adhesion have been deposited by wet chemical spin-coating technique on polished AISI 440C steel substrates. The as-deposited films (xerogel films) have been subjected to annealing for 1h at different temperatures ranging from 100 to 500°C in an argon atmosphere. The size growth of the nano-hemispheres increased from 8nm for xerogel film to 28nm for film annealed at 400°C. It was found that as the annealing temperature increased from 100 to 400°C, nano-hemisphere-like structures were formed, which in turn have shown increase in the water contact angle from 122° to 147° and oil (peanut) contact angle from 85° to 96°. No change in the water contact angle (122°) has been observed when the films deposited at room temperature were heated in air from 30 to 80°C as well as exposed to steam for 8 days for 8h/day indicating thermal stability of the film.