Ba(Zn0.3Co0.7)2Fe16O27 hexagonal ferrites have been prepared by sol-gel method. Effects of polyvinyl pyrrolidone (PVP) on crystalline phase, natural surface and electromagnetic properties were analyzed. The XRD patterns of samples with and without PVP added both showed the single phase of hexagonal ferrite. The particle thickness increased when PVP was added. Moreover, Ferrites prepared with 2.0g PVP added into the sol solution had lower complex permittivity. Addition of PVP can be an effective way to obtain the electromagnetic match of hexagonal ferrites.