A naturally occurring Cameroonian smectite clay has been grafted with trimethylpropylammonium groups and the resulting organoclay deposited as thin film onto a glassy carbon electrode (GCE) surface. It was then exploited as a suitable matrix for the accumulation and the electrochemical detection of ascorbic acid (AA) and uric acid (UA). Cyclic voltammetry revealed an increase in oxidation peak responses along with a negative shift of the corresponding anodic peak potential for both AA and UA species when using the organoclay coated GCE in comparison with the bare electrode. The electroanalytical response was improved by coating the electrode surface with a first layer of sublimed ferrocene (FCs), and then overcoating with the organoclay film to avoid the mediator leaching. The resulting bilayer film exhibited good characteristics such as extended linear range and high sensitivities for AA and UA, in cyclic voltammetry and amperometry. Interestingly, the redox mediator FCs was likely to lower overpotentials for AA oxidation (but not for UA), making possible the selective detection of these species in a mixture. The developed method could be used for the determination of AA in a pharmaceutical preparation and for UA in urine.