The direct mechanocatalytic Suzuki–Miyaura coupling reaction, utilizing palladium milling balls as active catalysts, was investigated regarding the physical state of the reagents and the reaction phase. The substitution patterns and functional groups of different aryl iodides were varied and different boronic acid derivates were utilized to achieve a wide range of substrate combinations. In the neat grinding experiments, liquid aryl iodides were more reactive than solid ones and a steric influence of the substituents, especially pronounced in ortho compounds, was observed. In order to overcome the general low reactivity of the solid phase, several liquid-assisted grinding experiments were conducted and the influence of substrate solubility and catalyst wettability analyzed. Among all LAG additives, EtOH showed the greatest impact on the reactivity, as it converts boronic acid derivatives into liquid and reactive esters under mechanochemical conditions, significantly speeding up the reaction.