Effects of alkali ceramics, Na₂ZrO₃ (NZ) and Li₄SiO₄ (LS), were quantified in the catalytic pyrolysis of sawdust, using thermogravimetric analysis and kinetic modeling. Results indicated that the alkali ceramics were able to initiate thermal decomposition at lower temperatures and enhanced H₂ yield. The mean activation energies estimated by Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO) and Friedman methods were within the range of 162–166, 114–116, 112–117 kJ mol^–1 for sawdust (SD), sawdust mixed with Li₄SiO₄ (SD-LS) and sawdust mixed with Na₂ZrO₃ (SD-NZ), respectively. The theoretical and experimental master plots constructed for SD closely match with theoretical master plot corresponding to three-dimensional diffusion (Ginstling–Brounshtein equation) (D4) reaction model. The SD-LS and SD-NZ samples followed first-order (F1) reaction model at lower conversions and shifted from F1 to three-dimensional diffusion (D4) reaction model at higher conversions.