The main objective of our work is to study the plasticizing effect of citrate esters on poly (lactic acid)/poly (ɛ-caprolactone) (PLA/PCL) blends. The samples were prepared by melt mixing in a plastographe Brabender, and followed by compression molding. The results obtained by differential scanning calorimetry (DSC), confirmed that the addition of the citrate ester resulted in a decrease of the glass transition temperature (Tg). The largest reduction was observed with blends by adding up to 30 wt% of the citrate plasticizer. Moreover, the incorporation of the monomeric plasticizers in the mixtures increases the plasticization of PLA by decreasing its tan δ obtained through the dynamic mechanical analysis (DMA). Thermogravimetric analysis (TGA), confirmed that the addition of the citrate plasticizer has promoted a decrease in thermal stability of PLA.