With the depletion of nonrenewable resources such as oil/coal/gas, more and more research studies began to focus on the high-value utilization of residual biomass resources. Herein, for the first time, honeycomb nanoporous microspheres fabricated from renewable biomass resources of cellulose were used as a carrier to fabricate a highly dispersed palladium (Pd) nanocatalyst. Various physicochemical characterizations presented convincing pieces of evidence for the good dispersion of Pd clusters with a mean diameter of 1.6 nm. As the carrier, cellulose microspheres with an interconnected nanoporous structure contributed to the adhesion and dispersion of Pd particles, and their rich hydroxyl groups could fix the Pd particles. Importantly, the cellulose matrix could in situ induce the formation of metallic Pd(0) during calcination without a reductant. The cellulose/Pd catalyst was applied to the Suzuki coupling reaction, which exhibited promising catalytic activity compared to commercial Pd/C and unsupported homogeneous Pd(OAc)2 catalysts, as well as good stability. The utilization of the residual biomass resource to build catalyst materials would be important for the sustainable chemistry.