In certain cases (CA•5, CA•9, CA•10, and CA•15), the resulting cocrystals did not exhibit the expected 1:1 stoichiometric ratio of the two components in the unit cell. These instances were beyond the scope of the present study, highlighting the complex relationship between solvent selection, stoichiometry, and crystallisation outcomes. For the remaining 13 combinations, successful co-crystallisation was achieved, maintaining the targeted stoichiometric ratio. Notably, six of these combinations (CA•4, CA•7, CA•8, CA•12, CA•17, and CA•20) produced polar cocrystals. Our investigation uncovered 16 previously unknown structures(Supplementary Fig. ). Remarkably, 8 of the 16 newly discovered cocrystals adopted polar space groups, meaning that 50% of the identified cocrystals are polar. This proportion significantly exceeds the statistical occurrence of polar cocrystals (~13.9%) reported in the CSD (Fig. ), highlighting the effectiveness of our workflow in discovering polar hydrogen-bonded cocrystals. With ongoing experimentation involving 5 different crystallization methods, both the number and frequency of polar cocrystals may continue to rise. Given their inherent piezoelectric properties, these polar cocrystals hold considerable promise for integration into compact, portable devices with applications in energy harvesting, as demonstrated in Supplementary Fig. .