Deposition techniques that can uniformly and conformally coat deep trenches and very high aspect ratio pores with uniform thickness films are valuable in the synthesis of complex three-dimensionally structured materials. Here it is shown that high pressure chemical vapor deposition can be used to deposit conformal films of II–VI semiconductors such as ZnSe, ZnS, and ZnO into high aspect ratio pores. Microstructured optical fibers serve as tailored templates for the patterning of II–VI semiconductor microwire arrays of these materials with precision and flexibility. In this way, centimeters-long microwires with exterior surfaces that conform well to the nearly atomically smooth silica templates can be fabricated by conformal coating. This process allows for II–VI semiconductors, which cannot be processed into optical fibers with conventional techniques, to be fabricated into step index and microstructured optical fibers.