The attributes of large‐amplitude Fourier transformed AC voltammetry have been assessed at electrodes constructed from either a single carbon fiber microdisk or a random assembly of carbon fiber microdisks (RAM). Factors that govern the limits of detection for the FcMeOH and uric acid analytes have been established. For the reversible FcMeOH oxidation process, the RAM electrode provides the lower limit of detection through substantial amplification of the peak current magnitude, and hence superior faradaic current‐to‐noise ratio. In contrast for the overall two‐electron oxidation of uric acid, the much faster electron transfer rate achieved at the electrochemically treated single carbon fiber microelectrode provides the lower detection limit, which is again optimal in the sixth harmonic.