Over the last few decades, bio-based polymers have attracted considerable attention from both academic and industrial fields regarding the minimization of the environmental impact arising from the excessive use of petrochemically-based polymeric materials. In this context, poly(ethylene vanillate) (PEV), an alipharomatic polyester prepared from 4-(2-hydroxyethoxy)-3-methoxybenzoic acid, a monomer originating from lignin-derived vanillic acid, has shown promising thermal and mechanical properties. Herein, the effects of three different catalysts, namely titanium butoxide (TBT), titanium isopropoxide (TIS), and antimony trioxide (Sb2O3), on the synthesis of PEV via a two-stage melt polycondensation method are investigated. The progress of the reaction is assessed using various complementary techniques, such as intrinsic viscosity measurement (IV), end group analysis (AV), nuclear magnetic resonance spectroscopy (NMR), Fourier-transformed infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). The thermal stability of the produced polyesters is studied by evolved gas analysis mass spectrometry (EGA-MS). Moreover, as the discoloration in polymers affects their applications, color measurement is performed here. Finally, theoretical kinetic studies are carried out to rationalize the experimental observations.