The objectives of our research are to investigate the concept of delignification from pinecone through alkaline fractionation and then extraction of formic acid from the hydrolysate through esterification using ethanol. The pinecone is considered a promising material because of its relatively higher lignin content (35.80%) than other lignocellulosic biomass. The recovery yield of acid insoluble lignin (AIL) reached its maximum value of 79.20% at 8% NaOH, and the concentration of formic acid in the hydrolysate had its highest value under the same conditions. Moreover, the glucan content in fractionated solid remained high. The hydrolysate was subjected to esterification with ethanol under various reaction conditions for formic acid extraction, with solvent mixing ratio range: 1:1-1:4 v/v, reaction temperature range: 30-45 degrees C, and reaction time range: 60-100 min. Subsequently, the ethanol mixture (ethanol and ethyl formate) was recovered through distillation. The formic acid was extracted with more than 85% at mixing ratio of 1:2 and 45 degrees C for all reaction times. Furthermore, salt compounds composed mainly of Na and S were recovered because of its properties not soluble in ethanol solution.