Pine-fruit shell (PFS) is a lignocellulosic residue derived from the fruit of Araucaria angustifolia, a coniferous tree native of South America, part of a whole vegetation of the Atlantic Forest, found in the South and Southwest of Brazil. In this work PFS will be characterized and used in the production of PFS-based polyols through oxypropylation. Three series were chosen (PFS/propylene oxide (PO) (w/v, g/mL) of 30/70, 20/80 and 10/90) with four catalyst levels (5%, 10%, 15% and 20%, (w/w, PFS based)). Oxypropylation occurred at moderate conditions of temperature, pressure and time giving rise to liquid polyols with a homopolymer content (PPO) ranging from 4-65%, a hydroxyl number (IOH) between 257-605 mg KOH/g and viscosities (V) varying from 0.76 Pa.s to 373.90 Pa.s (20°C) for the series 20/80 and 10/90, while for the series 30/70, the viscosity reached values higher than 500 Pa.s, 20C. The unreacted PFS (UR) varied between 3.6% and 77.4% (PFS-basis). After the PFS-based polyols production and characterization, a principal component analysis (PCA) was performed in order to evaluate the established interactions between the used formulation variables and the obtained polyol properties. The PCA analysis allowed to clarify the interactions between PFS and PO contents and the final biopolyol properties (PPO, IOH, V and UR). This approach showed to be a simple method to rationally analyze the influence of the input formulation variables on the final polyol properties.