Modern organic synthesis is highly demanding for environmentally friendly biosourced solvents. In this area, alkyl levulinates, that can be obtained directly from lignocellulose, represent serious candidates. This was demonstrated for the first time in this study, using Heck C−C coupling in the presence of various heterogeneous Pd‐catalysts. In most cases quantitative conversions of aryl halides were observed within short reaction time, associated with good to high isolated yields (30‐95%). In addition to be suitable solvents for this application, alkyl levulinates can be recovered and reused, offering when associated to heterogeneous catalysts facile work‐up procedure for easy obtaining of pure products.