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The smart choice of polyoxometalates (POMs) and the design of POM@carbon-based composites are promising tools for producing active electrocatalysts for both the oxygen reduction (ORR) and the oxygen evolution reactions (OER). Hence, herein, we report the preparation, characterization and application of three composites based on doped, multi-walled carbon nanotubes (MWCNT_N6) and three different POMs (Na₁₂[(FeOH₂)₂Fe₂(As₂W₁₅O₅₆)₂]·54H₂O, Na₁₂[(NiOH₂)₂Ni₂(As₂W₁₅O₅₆)₂]·54H₂O and Na₁₄[(FeOH₂)₂N_i2(As₂W₁₅O₅₆)₂]·55H₂O) as ORR and OER electrocatalysts in alkaline medium (pH = 13). Overall, the three POM@MWCNT_N6 composites showed good ORR performance with onset potentials between 0.80 and 0.81 V vs. RHE and diffusion-limiting current densities ranging from −3.19 to −3.66 mA cm⁻². Fe₄@MWCNT_N6 and Fe₂Ni₂@MWCNT_N6 also showed good stability after 12 h (84% and 80% of initial current). The number of electrons transferred per O₂ molecule was close to three, suggesting a mixed regime. Moreover, the Fe₂Ni₂@MWCNT_N6 presented remarkable OER performance with an overpotential of 0.36 V vs. RHE (for <i>j</i> = 10 mA cm⁻²), a <i>j</i>_max close to 135 mA cm⁻² and fast kinetics with a Tafel slope of 45 mV dec⁻¹. More importantly, this electrocatalyst outperformed not only most POM@carbon-based composites reported so far but also the state-of-the-art RuO₂ electrocatalyst. Thus, this work represents a step forward towards bifunctional electrocatalysts using less expensive materials.