The presence of N,N-dimethylacrylamide (NDA) influences the stability of initial, clear, single-phase Winsor IV inverse microemulsion composed of toluene/AOT (sodium salt of bis(2-ethylhexyl) sulfosuccinate)/NDA/water/acrylamide (AAm). For a molar fraction of NDA, n(NDA) = [NDA]/([NDA] + [AAm]) = 0.200 a single-phase system turned to a milky one during polymerization initiated by oil-soluble dibenzoyl peroxide or water-soluble ammonium peroxodisulfate, and finally a two-phase system was formed. For nNDA values greater than 0.200 also the precipitation of a polymeric product was observed during polymerization. The (co)polymerization rate of AAm and NDA exponentially decreases with increasing value of nNDA, while the reverse is true for the (co)polymer particle diameter. The results support the idea of simultaneously proceeding free-radical polymerization initiated by free radicals in continuous oil and dispersed water phase of the inverse microemulsion system.