Mechanical pencil leads were studied as disposable, low-cost electrodes. Lateral surfaces of mechanical pencil leads branded as “polymer” show high electron transfer rates for hexaamineruthenium chloride, potassium ferricyanide, ascorbate, ferric chloride and dopamine electrochemical probes, and are significantly better electrode materials than either classic woodcase clay–graphite pencil compositions or non-polymer mechanical pencil leads. Best polymer leads outperform glassy carbon, basal and edge graphite and boron-doped diamond electrodes. In addition to electrochemical experiments, the studied pencil leads were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy and Raman spectroscopy. High content of sp3 hybridized carbon (up to 80%) with a low degree of surface oxidation and occurrence of silicon monoxide (SiO) on the surfaces of the polymer pencil leads were found using X-ray photoelectron spectroscopy. Low double layer capacitance values of similar magnitude as that found for boron-doped diamond electrodes are at the origin of favourably low background currents on the polymer pencil lead electrodes. SiO containing polymer pencil lead electrodes allow electrochemical analysis that is more sensitive than common carbon electrodes, as demonstrated by voltammetry of adenine and xanthine.