Graphite powder-supported nickel(II) hexacyanoferrate (NiHCF) was prepared by the in situ chemical deposition method and then dispersed into methyltrimethoxysilane-derived gels to form a conductive composite. The composite was used as electrode material to construct a surface-renewable three-dimensional NiHCF-modified carbon ceramic electrode. Electrochemical behavior of the chemically modified electrode was well characterized using cyclic and square-wave voltammetry. The electrode presented a good electrocatalytic activity toward the oxidization of thiosulfate and thus was used as an amperometric sensor for thiosulfate in the photographic waste effluent. In addition, the electrode exhibited a distinct advantage of surface-renewal by simple mechanical polishing, as well as simple preparation, good chemical and mechanical stability.