Nanoporous cobalt‐nickel phosphate VSB‐5 molecular sieve (CoVSB‐5) was synthesized by conventional heating for 48 h in the presence of (2‐hydroxyethyl) trimethylammonium hydroxide as template. Then, a novel, cheap and efficient catalyst was developed for formaldehyde electrooxidation by decorating Ni2+ ions on the surface of CoVSB‐5 modified carbon paste electrode (CoVSB‐5/CPE). The electrochemical behavior of the Ni‐CoVSB‐5/CPE electrode towards the formaldehyde oxidation was evaluated by cyclic voltammetry (CV) as well as chronoamperometry methods. An oxidation peak was observed at 0.60 V in 0.1M NaOH solution for electrocatalytic oxidation of formaldehyde with EC′ mechanism. It has been observed that CoVSB‐5 at the surface of CPE can improve catalytic efficiency of the dispersed nickel ions toward oxidation of formaldehyde. The values of electron transfer coefficient, the mean value of catalytic rate constant and diffusion coefficient for formaldehyde and redox sites were obtained to be 0.66, 1.80 × 105 cm3 mol−1 s−1 and 3.62 × 10−4 cm2 s−1, respectively. Obtained results from cyclic voltammetry (CV) and chronoamperometry techniques specified that the electrode reaction is a diffusion‐controlled process. The good catalytic activity, high sensitivity, good selectivity and stability and easy in preparation rendered the Ni‐CoVSB‐5/CPE to be a capable electrode for formaldehyde electrooxidation.