This paper presents systematic analysis of value creation chains and their economic and environmental hotspots within a multi-product biorefinery with the primary goal to promote sustainable biorefining. Lignocellulosic biorefinery producing ethanol, crude lignin oil (CLO) and electricity was analysed. The methodology involves transformation of technological model into an input-output one with the use of matrix notation for the analysis of economic and environmental attributes along value chains. The results show that the accumulation of biomass through energy supply grows by a factor of 1.2 for ethanol and electricity, and by 1.4 for CLO value chains, of which solid recovery, lignin solvolysis and biomass pretreatment are responsible for the most significant growth indicating the necessity for energy optimization of those steps. The analysis reveals a superfluous role of infrastructure in pretreatment and lignin drying processes. Of infrastructural costs related to the equipment required for the pretreatment step, wastewater treatment (WWT) facility is responsible for 58%, and of the costs of lignin drying, the combined heat and power plant is responsible for 56%. WWT determines 75% of infrastructural GHG emissions attributable to pretreatment, and 57% of those related to lignin drying. This points at an advantage of a biorefinery concept involving the removal of lignin fraction before the valorization of carbohydrates. Another hotspot, the lignin solvolysis technology, shows environmental and economic advantages of its further optimization in terms of production costs and GHG emissions. The proposed method is helpful for analyzing economic and environmental hotspots in new biorefinery concepts and integration pathways.