Proton dissociation assisted negative polarity of malonic acid molecules admist glycine zwitterions leads to orgination of γ nucleation in the solution. Alteration in the nucleation behaviour and segregation of glycine polymorphs in the presence of malonic acid over a wide range of concentrations has been investigated both by experimental and analytical approaches. Complete changeover in the nucleation behaviour from 100% α to 100% γ is observed at the critical concentration of the additive. Shifting in the overall charge environment of the system towards cationic in the presence of malonic acid favours the nucleation of γ through induced charge compensation in the solution. Tuning of merohedral twinning in γ nucleation by the additive concentration has been well revealed in the present work. CNT based analytical approach employed elucidates well the experimental observations through the estimated interfacial energy, volume excess free energy, critical radius, activation energy barrier and nucleation rates of α and γ polymorphs. Structural affirmation of the nucleated polymorphs was carried out by powder x‐ray diffraction.