The present invention provides apparatus, kits and methods for assaying analytes using photoelectrochemical molecules as labels. Specifically, the present invention provides a method for assaying an analyte, comprising: a) contacting a sample suspected of containing an analyte with a reactant capable of binding and/or reacting with the analyte under suitable conditions to allow binding of analyte, if present in the sample, to the reactant; and b) assessing binding and/or reacting between the analyte and the reactant to determine presence and/or amount of analyte in the sample, wherein the reactant, analyte, or additional reactant or additional analyte or analyte analog is labeled with a photoelectrochemically active molecule. The assessing step also comprises converting the photoelectrochemically active molecule with light to an excited state in the presence of an electrode, and assessing an electric current generated by an electron transfer between the excited photoelectrochemically active molecule and the electrode.