The present study investigated if new biocomposite materials, polyurethanes (PURs) added with functionalized cellulose fibers, produce potential toxic effects on two target organisms currently used in biomonitoring the quality of two different environmental compartments. Natural fibers were extracted from the species Spartium junceum L., a shrub commonly found in the southern region of the Mediterranean having a high cellulose content. All PURs produced were characterized by Fourier-transform infrared spectroscopy, and their structure was analyzed by scanning electron microscopy. We measured the effects of exposure to aromatic and aliphatic PUR composites (containing or not cellulose fibers) on the aquatic model organism Daphnia magna Straus, a freshwater crustacean (Cladocera), and a biomonitor of air quality, the fruticose epiphytic lichen Pseudevernia furfuracea (L.) Zopf. Leachates from aliphatic PUR composite not containing cellulose are more toxic to D. magna than all others, showing a slight acute toxicity in the case of the shortest exposure (24 h) and a moderate acute toxicity in the longer one (48 h). This effect is most likely due to the presence of free organic ammines and amides, which, in their turn, are immobilized in composites containing cellulosic fibers because of the considerable amount of chemical functional groups. Regarding lichens, both types of aliphatic PURs resulted in a toxic effect. Formulate not added with cellulose strongly promoted fungal peroxidation, whereas that which was functionalized affected the pigment concentration of the algal partner. Our results suggest that the use of cellulose in PUR production, in general, can limit the ecotoxicological effects on both test organisms and reduce the potential environmental impact due to this type of polymer.