The present study describes a two-step synthesis process for the cobalt complex of tetra-2,3-(5,6-di-tert-butyl-pyrazino) porphyrazine (tBu-TPyzPzCo). The product was ultrasonically impregnated onto carbon black (CB) to prepare a supported catalyst (tBu-TPyzPzCo/CB). We built a split photoelectric catalytic device to test the performance of photocatalytic, electrocatalytic and photoelectrocatalytic degradation of partially hydrolyzed polyacrylamide (HPAM). The results confirm that HPAM exhibited more efficient degradation in the presence of a supporting catalyst using the photoelectrocatalytic process than by photocatalytic or electrocatalytic oxidation—or even the sum of the two in saline water. The photoelectrocatalytic reaction confirmed that the process conforms to quasi-first order reaction kinetics, while the reaction rate constants were 6.03 times that of photocatalysis and 3.97 times that of electrocatalysis. We also compared the energy consumption of the three processes and found that the photoelectrocatalytic process has the highest energy efficiency.