Two independent spectroscopic methods are presented and compared for the quantitation of the phenolic hydroxyl groups in lignins. The combined information is used to further elucidate the character of the lignin samples examined. The UV method is based on the difference of the spectroscopic properties of the ionised and the nonionised phenol. The method using 1H NMR spectroscopy is based on the exchange of phenolic protons in D2O. The difference in integrated proton intensities in the sample dissolved in DMSO and the sample with additional 20% D2O is proportional to the phenolic protons. The method based on UV spectroscopy uses differences in the maxima close to 300 nm and 350 nm of the sample dissolved in alkali and the neutral sample. The results using the two independent methods are in agreement for milled wood lignin, for kraft lignin and for model compounds carrying one aromatic hydroxyl group. For modified lignins and for model compounds with more than one aromatic hydroxyl group, the UV method gives too low values for phenolic hydroxyl groups. The combined results obtained by the two methods however provide information of the total amount of the phenolic groups and of the nature of the phenolic structure formed by the lignin refining.