Single-stranded deoxyribonucleic acid (ssDNA) with guanine-rich sequences can form four-stranded structures so called G-quadruplex (Gq), which binds hemin, an iron-containing porphyrin. The hemin/Gq is an electroactive complex and exhibits peroxidase activity, and thus the hemin/Gq complexes have attracted great attention as a signal generator. This short review surveys the use of the hemin/Gq complex as an electrochemical signal generator. Electrochemical methods for detecting the hemin/Gq complex, approaches to signal amplification, and targeting strategies are herein discussed. Compared with protein-based signal generators, hemin/Gq complexes have some advantages: a wide variety of ssDNA sequences with various chemical modifications are easy to obtain, they can be immobilized on an electrode easily, and they can be designed as desired to connect functional domains. Also there are many molecular-biological tools to handle them. Hemin/Gq complexes have been successfully used to detect bioanalytes ranging from low molecular weight compound to macromolecules such as proteins, specific nucleic acids, or living cancer cells. Such bioanalytes are critical to the investigation of cellular function. Thus, DNAbased probes that contain hemin/Gq as a signal generator are a promising tool for the electrochemical analysis of cellular function, offering a competent alternative to a conventional protein-based signal generator.