Abstract This study aims to identify potential bio‐based derivatives from the conversion of platform chemicals at early design phases. To do this, an existing early‐stage sustainability assessment method was extended, to cover both catalytic and biochemical conversion processes in biorefinery systems. The method combines proxy indicators describing economic, environmental, and operational aspects. Conversion routes are analyzed by using three case studies: catalytic conversion of bio‐based syngas to derivatives with petrochemical counterpart (16 systems), biochemical conversion of carbohydrates to derivatives with petrochemical counterpart (12 systems), and biochemical and catalytic conversion of glycerol to derivatives with petrochemical counterpart (8 systems). The indicators were combined into a single score, and then compared to a petrochemical counterpart. Sensitivity analysis was carried‐out to analyze the influence of conversion yields and prices on the index ratio. Furthermore, scenario analyses were conducted to account for three different regions (the EU , the USA , and China). Results confirmed the successful application of the method to processes that considered catalytic and/or biochemical conversion processes. The method showed to be an effective tool for the selection of bio‐based derivatives with favorable potential sustainability performances in comparison to their petrochemical counterparts. The results show two systems from syngas, five systems from carbohydrates, and seven systems from glycerol as favorable. The results serve as a primary database to draw recommendations on e.g., future configurations of integrated biorefineries. © 2015 Society of Chemical Industry and John Wiley & Sons, Ltd