Herein, we report a shape-controlled preparation of Praseodymium hexacyanoferrate (PrHCF) using a simple electrochemical technique. The electrochemically fabricated PrHCF modified glassy carbon electrodes (GCE) shows an excellent electrocatalytic activity towards sulfite oxidation. The morphology of PrHCF particles were controlled by carefully changing various synthesis conditions including electrochemical technique (cyclic voltammetry, amperometry and chemical), cations in the supporting electrolyte (K+, Na+, Li+ and H+), deposition cycles, molar ratio of precursors, and applied potential (-.2,0 and 0.2 V). The morphologies of the PrHCF was elucidated using scanning electron microscopy (SEM). The as-synthesized PrHCF was characterized using X-ray diffraction pattern (XRD), Infra-red (IR) and energy dispersive X-ray spectroscopy (EDX). The electrochemical oxidation of sulfite on PrHCF modified GCE was investigated using cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The sensitivity of the as-developed sulfite sensor was determined to be 0.036 mu A mu M(-1)cm(-2). The low limit of detection was determined to be 2.15 mu M. The real time application of PrHCF modified GCE was confirmed through the determination of sulfite from red wine and tap water samples. (C) 2015 Elsevier Ltd. All rights reserved.