The efficient utilization of lignin from the papermaking black liquor has attracted interest due to its carbon-neutral value and industrial application. This work illustrates a simple support-phosphate-pretreatment strategy to develop superdispersed Ni species in activated carbon (AC) to enhance the hydrodeoxygenation (HDO) reactions of the lignin model compound guaiacol into biohydrocarbons under alkaline conditions. For the first time, sodium polyphosphate was applied as a pretreatment agent for coconut carbon in the synthesis of carbon-supported Ni catalysts. Superdispersed Ni nanoparticles were achieved on Ni/NaPnOAC with a particle size of 2.5 nm, which was much smaller than that on unmodified Ni/C (13.1 nm). The characterization results and reactions revealed that the P−O that formed served as anchoring sites for the Ni species and strengthened the interaction between the Ni species and support (SMSI), which resulted in significantly improved dispersion of the Ni metal sites and, thus, a nearly 6-fold greater yield of hydrocarbons was obtained on Ni/NaPnOAC (58.1%) than on Ni/C (10.1%). In addition, compared with Ni2P/NaPnOAC and NiS/NaPnOAC, Ni/NaPnOAC exhibited higher HDO activity, especially higher direct deoxygenation (DDO) activity and higher benzene yield, reducing hydrogen consumption during the HDO reaction.