Multicomponent materials, where nanosized selenium (Se) is dispersed in polymer matrices, present as polymer nanocomposites (NCs), namely, selenium polymer nanocomposites (SeNCs). Selenium as an inorganic nanofiller in NCs has been extensively studied for its biological activity. More ecologically safe and beneficial approaches to obtain Se-based products are the current challenge. Biopolymers have attained great attention with perspective multifunctional and high-performance NCs exhibiting low environmental impact with unique properties, being abundantly available, renewable, and eco-friendly. Composites based on polysaccharides, including beta-glucans from edible and medicinal mushrooms, are bioactive, biocompatible, biodegradable, and have exhibited innovative potential. We synthesized SeNCs on the basis of the extracellular polysaccharides of several medicinal mushrooms. The influence of bio-composites from mushrooms on potato plant growth and tuber germination were studied in two potato cultivars: Lukyanovsky and Lugovskoi. Bio-composites based on Grifola umbellata demonstrated the strongest positive effect on the number of leaves and plant height in both cultivars, without negative effect on biomass of the vegetative part. Treatment of the potato tubers with SeNC from Gr. umbellata also significantly increased germ length. Potato plants exposed to Se-bio-composite from Ganoderma lucidum SIE1303 experienced an increase in the potato vegetative biomass by up to 55% versus the control. We found earlier that this bio-composite was the most efficient against biofilm formation by the potato ring rot causative agent Clavibacter michiganensis subsp. sepedonicus (Cms). Bio-composites based on Pleurotus ostreatus promoted increase in the potato root biomass in the Lugovskoi cultivar by up to 79% versus the control. The phytostimulating ability of mushroom-based Se-containing bio-composites, together with their anti-phytopathogenic activity, testifies in favor of the bifunctional mode of action of these Se-biopreparations. The application of stimulatory green SeNCs for growth enhancement could be used to increase crop yield. Thus, by combining myco-nanotechnology with the intrinsic biological activity of selenium, an unexpectedly efficient tool for possible applications of SeNCs could be identified.