New composite materials were developed with poly(lactide) (PLA) and Posidonia oceanica fibers through reactive extrusion in the presence of dicumyl peroxide (DCP) and subsequent injection molding. The effect of different amounts of methyl trans-cinnamate (MTC) on the mechanical, thermal, thermomechanical, and wettability properties was studied. The results showed that the presence of Posidonia oceanica fibers generated disruptions in the PLA matrix, causing a decrease in the tensile mechanical properties and causing an impact on the strength due to the stress concentration phenomenon. Reactive extrusion with DCP improved the PO/PLA interaction, diminishing the gap between the fibers and the surrounding matrix, as corroborated by field emission scanning electron microscopy (FESEM). It was observed that 20 phr (parts by weight of the MTC, per one hundred parts by weight of the PO/PLA composite) led to a noticeable plasticizing effect, significantly increasing the elongation at break from 7.1% of neat PLA to 31.1%, which means an improvement of 338%. A considerable decrease in the glass transition temperature, from 61.1 °C of neat PLA to 41.6 °C, was also observed. Thermogravimetric analysis (TGA) showed a loss of thermal stability of the plasticized composites, mainly due to the volatility of the cinnamate ester, leading to a decrease in the onset degradation temperature above 10 phr MTC.