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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‐50.6 (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.

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