Calcium lignosulfonate as a biopolymer component was incorporated into acrylonitrile butadiene rubber in the amount-50 phr. Four low-molecular organic molecules-1,4-butanediol, ethylene glycol, and two glycerols with different purity-were used as plasticizers. They were applied in rubber compounds in the amount ranging from 5 to 30 phr. The influence of the plasticizers on the curing process, cross-link density, morphology, and physical-mechanical properties was investigated. The blooming of plasticizers was also under observation. The results revealed that the application of plasticizers resulted in the deceleration of the curing kinetics and reduction in torque increments, pointing to the decrease in the rubber compounds' viscosity. This was subsequently confirmed by the rheological measurements. The plasticizers softened the rubber matrix as well as the biopolymer filler. The higher the polarity of the plasticizer, the higher the plasticizing effect on lignosulfonate. The plasticizing effect increased in the following order: 1,4-butanediol <
ethylene glycol <
glycerols. Softened lignosulfonate formed small, soft filler-like domains well distributed within the rubber matrix. Good compatibility and adhesion between the rubber and the biopolymer on their interface was observed, leading to the enhancement in the tensile characteristics of the vulcanizates plasticized with ethylene glycol and glycerols.