The fixed bed gasification of lignin rich and deficient mixtures was carried out to probe the synergistic effects between two model compounds, Lignin Pink (LP) rich in Na and Cellulose Microcrystalline (CM). Reaction conditions utilized the most commonly used air ratios in current wood gasifiers at 750 °C and 850 °C. It was found that by increasing the lignin content in the mixture, there was a selectivity change from solid to gas products, contrary to a similar study previously carried out for pyrolysis. This change in product mix was promoted by the catalytic effect of Na edge recession deposits on the surface of the char. As a result, the water gas shift reaction was enhanced at 850 °C for the LP48CM52 mixture across all air ratios, this was evidenced by a strong correlation between the produced H2 and COx. Meanwhile, by lowering the lignin content in the mixtures, the reactivity of cellulose microcrystalline was found to generate more char at higher temperature, similar to lignin mixtures when undergoing pyrolysis.