The screening and early diagnosis of diseases are crucial for a patient’s treatment to be successful and to improve their survival rate, especially for cancer. The development of non-invasive analytical methods able to detect the biomarkers of pathologies is a critical point to define a successful treatment and a good outcome. This study extensively reviews the electrochemical methods used for the development of biosensors in a liquid biopsy, owing to their ability to provide a rapid response, precise detection, and low detection limits. We also discuss new developments in electrochemical biosensors, which can improve the specificity and sensitivity of standard analytical procedures. Electrochemical biosensors demonstrate remarkable sensitivity in detecting minute quantities of analytes, encompassing proteins, nucleic acids, and circulating tumor cells, even within challenging matrices such as urine, serum, blood, and various other body fluids. Among the various detection techniques used for the detection of cancer biomarkers, even in the picogram range, voltammetric sensors are deeply discussed in this review because of their advantages and technical characteristics. This widespread utilization stems from their ability to facilitate the quantitative detection of ions and molecules with exceptional precision. A comparison of each electrochemical technique is discussed to assist with the selection of appropriate analytical methods.