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.