Triethyl citrate (TEC), a non-toxic plasticizer, was synthesized by esterification of renewable citric acid (CA, from entire waste of oranges) with ethanol over modified H-ZSM-5 (HZ-5) zeolite. Different micro-meso composites (M-HZ-5) with varying crystallinities were prepared by alkaline treatment of HZ-5. M-HZ-5(0.6) (87% crystallinity) was observed to be a potential and environmentally benign catalyst with 96% CA conversion, 64% TEC selectivity (61.44% TEC yield), and a reusability of six cycles. The probable catalytic mechanism of esterification was also proposed.