The modification of carbon cloth (CC) with Prussian blue (PB) and chitosan (CS) leads to the elaboration of a composite electrode (PB/CS/CC), employed to electrocatalyze the oxidation of ascorbic acid (AA). This electrode exhibits great performances towards the AA detection, thanks to the good conductivity of CC and the efficient catalytic properties of PB. The modified electrode shows a rapid response of less than 2 s, a very high sensitivity of 1.64 A ⋅ M−1 and a good resistance towards common interferences. Its linear range goes from 3×10−7 M to 3×10−4 M (R2=0.993), with a detection limit (S/N=3) of 2.50×10−7 M. Finally, such electrode can detect AA in commercial vitamin C; it is thus a good candidate as a simple and convenient sensor for general applications.