One of the next‐generation structural materials is carbon foam. Porous materials have become an intriguing alternative material to traditional ones in many utilizations based on their light weight and incomparable properties. Coal or fossil oils are conventionally used to produce pitch, phenolic resin, and polyurethane as carbon foam precursor. Biomass liquefaction is a developing technique to convert biomass resources into the industrial chemicals. In this study, spruce tree sawdust was liquefied under mild conditions with different solvent type (phenol or phenol + bio‐oil mixture). The unique aspect of this work is the synthesis of bio‐polyol when pyrolytic oil is used as an alternative to phenol in the solvolysis reaction and its evaluation in carbon foam production with multilayer graphene sheets. Therewithal, the ratios of biomass to solvent were 1/3 as well as 1/5, and the comparison of product characteristics is another originality of the study. Slow pyrolysis of spruce tree sawdust was performed under static atmosphere and bio‐oil was characterized with elemental analysis and various chromatographic and spectroscopic techniques. The effect of mass ratio of biomass/solvent on the characteristics of porous resin foams synthesized from liquefaction product. Obtained resin foams were carbonized at 400 °C, and then activated at 800 °C under nitrogen atmosphere. Structure evaluation of resin foams, carbonized foams, and activated carbon foams from liquefied spruce tree sawdust was investigated by using elemental analysis, x‐ray diffraction, nitrogen adsorption/desorption isotherms, scanning electron microscopy, true/bulk density, and compressive strength tests. Although the surface area values decreased when bio‐oil was added as a solvent, it was determined that the compression strengths of the produced carbon foams (up to 1.080 MPa) were higher than that of conventional phenolic foams. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47185.