Syngas, bio-oil, and biochar are three-phase products yielded from biomass pyrolysis. As a clean fuel, syngas has great potential value within the background of carbon neutrality. However, little attention has been paid to syngas compared with other pyrolysis products. In this study, a novel method for high yield production of syngas with high calorific value production has been proposed, in the context of light bio-oil (LB) leached bamboo and heavy bio-oil (HB) co-pyrolysis. The effects of three experimental variables (mass ratio, pyrolysis temperature, and residence time) on the yield and properties of syngas were investigated using response surface methodology. Results showed that under the typical experimental conditions (mass ratio 1:1, 550 degrees C, and residence time of 17.5 min), the experimental gas yield (23.14 wt%) and H-2 + CO content (41.18 vol%) of HB and raw bamboo co-pyrolysis were 4.87 wt% and 2.24 vol% higher than the theoretical value, respectively. Notably, LB leaching pretreatment effectively removed biomass ash and changed the pyrolysis pathway. A more significant synergistic effect was observed during the co-pyrolysis of HB and LB leached bamboo, leading to a higher gas yield and a higher combustible gases content. High-quality syngas enriched in H-2 and CO was obtained. Under the optimal conditions (mass ratio 1:3.09, 700 degrees C, and residence time of 19 min), the yield of syngas was up to 42.92 wt% with a high HHV of 19.26 MJ/Nm(3), and the H-2 + CO content was 63.74 vol%. Eventually, the regression equations between syngas properties and variable values were obtained. The method proposed in this study could herein provide a basis for the utilization of different fractions of bio-oil, as well as the co-pyrolysis for high quality syngas production.