The understanding of amorphous and heterojunction materials has been widely used in the field of electromagnetic wave absorption due to their unique physical and chemical properties. However, the effectiveness of individual strategies currently used is still limited. Well-designed compositions and amorphous structures simplify the effect of different polarization mechanisms on the absorption of electromagnetic waves. In this work, through the carbonization and controlled phosphating of one-dimensional Co Metal-Organic Framework (Co-MOF) nanorods, the synthesis of complex components and amorphous CoP with phosphorus vacancies is successfully accomplished, thus adjusting the optimization of electromagnetic parameters. Phosphorus-vacancy-induced defective polarization loss and enhanced-electronegativity-differences-induced dipole polarization loss synergistically as a dual-polarization strategy significantly improved the electromagnetic parameters and impedance matching. In conclusion, the electromagnetic parameters of the Co@CoP@C composites are indeed significantly regulated, with reflection losses of -55 dB and a bandwidth of up to 5.5 GHz. These innovative research ideas provide instructive thinking for the development of amorphous absorbers with vacancies.