A scheme is described for measuring electron transfer kinetics between a surface-immobilized redox monolayer and a high temperature superconductor (HTSC) electrode at temperatures above and below the superconductor transition temperature T-c. The scheme depends on coating the HTSC electrode with an ultrathin metal film (Au, Ag) onto which redox monolayers of ferroceneoctanethiol with octanethiol diluent are co-chemisorbed by self-assembly. The ferrocene redox moiety is separated from the metal film/HTSC by an alkane chain tunneling barrier. Cyclic voltammetry and potential step electron transfer rate measurements are given for monolayer coated HTSC/Au film and HTSC/Ag film electrodes at temperatures above and below the 119 K T-c of the Tl2Ba2CaCu2O8 (Tl-2212) superconductor employed as the HTSC/metal electrode. The ferrocene monolayers display well-defined voltammetry down to 105 K. While the electron transfer rate measurements are estimates only, the voltammetry and rate measurements are the first of their kind for a molecular monolayer on an electrode in the superconducting state. The results will guide adjustment of the alkane chain tunneling barrier to a length appropriate for slower and more accurate electron transfer rate measurements, even at applied overpotentials large enough to reduce the electron transfer barrier to values smaller than the electron-pairing energy.