A rapid method for the quantitative determination of the hydroxyl value (OHV) of palm-based polyols by Attenuated Total Reflectant-Fourier Transform Infra-red Spectroscopy (ATR-FTIR) with partial least square regression (PLS) was developed. Calibration standards were based on 25 palm-based polyols, synthesised in the Advanced Oleochemical Technology Division (AOTD), Malaysian Palm Oil Board (MPOB) covering OHV values ranging from 59 to 229 mg KOH g^-1 of sample. The OHV values were also determined using AOCS Cd 13-60 standard method. The FTIR-generated calibration plot had a correlation coefficient (R²) of 0.9925 and a standard error of calibration (SEC) of 5.58, while the validation plots had R² of 0.9884 and standard error of prediction (SEP) of 5.35.