Agricultural waste, which is produced in large quantities annually, can be a threat to the environment. Biochar (BC) production represents a potential solution for reducing the amount of grapevine pruning residues and, accordingly, the impact on the environment and climate change. Biochar produced by the process of pyrolysis from grapevine pruning residues was investigated and characterized to be applied as an adsorbent of polyphenolic compounds with the aim of using the waste from viticultural production to obtain a quality product with adsorption and recovery potential. Standards of caffeic acid (CA), gallic acid (GA), and oleuropein (OLP) were used as polyphenolic representatives. The obtained data were fitted with the Langmuir and Freundlich isotherms models to describe the adsorption process. The best KL(0.39) and R2(0.9934) were found for OLP using the Langmuir model. Furthermore, the adsorption dynamics and recovery potential of BC were investigated using an adapted BC column and performed on an HPLC instrument. The adsorption dynamics of biochar resulted in the adsorption of 5.73 mg CA g−1of BC, 3.90 mg GA g−1of BC, and 3.17 mg OLP g−1of BC in a 24 h contact. The online solid phase extraction of the compounds performed on an HPLC instrument yielded a recovery of 41.5 ± 1.71% for CA, 61.8 ± 1.16% for GA, and 91.4 ± 2.10% for OLP. The investigated biochar has shown a higher affinity for low-polar compound adsorption and, consequently, a higher polar compound recovery suggesting its potential as an efficient polyphenolic compound adsorbent.