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The potassium dual-ion batteries (DIBs) have been attracting a great attention in recent years due to their promising environmental benignancy, high energy density, and long lifespan. The active materials based on conversion reaction mechanism are favorable and widely expected to alleviate the dendrite formation, red phosphorous was thus employed and fabricated into a three-dimensional porous carbon matrix anchored by P– O –C chemical bonding using vaporization–condensation–conversion process. Meanwhile, the elements modified carbon can not only guarantee the electronic conductivity and ions diffusion, but also alleviate the red phosphorous volumetric expansion and detachment. When coupled with graphite, the K-DIBs demonstrate excellent electrochemical performance with a high 213 Wh kg−1 energy density and a promising stability up to 650 cycles. This explored material will provide highly relevant insights for next-generation advanced energy storage systems. • New explored red phosphorous structure for potassium dual-ion batteries. • Inducing P– O –C chemical bonding to anchor red phosphorous for electronic conductivity and structure stability. • Excellent energy density of 213 Wh kg−1 and superior lifespan up to 650 cycles. [ABSTRACT FROM AUTHOR]