This paper reports a study of the chemical composition of the water-soluble (WS) fraction obtained by cold water precipitation of two commercial wood pyrolysis oils (BTG and Amaron). The fraction studied accounts for between 50.3 and 51.3 wt % of the oils. With the most common analytical techniques used today for the characterization of this fraction (KF titration, GC MS, hydrolyzable sugars, and total carbohydrates), it is possible to quantify only between 45 and 50 wt % of the fraction. Our results confirm that most of the total carbohydrates (hydrolyzable sugars and nonhydrolyzable) are soluble in water. The ion chromatography hydrolysis method showed that between 11.6 and 17.3 wt % of these oils were hydrolyzable sugars. A small quantity of phenols detectable by GC MS (between 2.5 and 3.9 wt %) were identified. It is postulated that the unknown high molecular weight fraction (30-55 wt %) is formed by highly dehydrated sugars rich in carbonyl groups and WS phenols. The overall content of carbonyl, carboxyl, hydroxyl, and phenolic compounds in the WS fraction was quantified by titration, the Folin Ciocalteu method, P-31 NMR, and H-1 NMR. The WS fraction contains between 5.5 and 6.2 mmol/g carbonyl groups, between 0.4 and 1.0 mmol/g carboxylic acid groups, between 1.2 and 1.8 mmol/g phenolic -OH, and between 6.0 and 7.9 mmol/g of aliphatic alcohol groups. Translation into weight fractions of the WS was done by supposing surrogate structures for the water-soluble phenols, carbonyl groups, and carboxyl groups, and we estimated the content of WS phenols (21-27 wt %), carbonyls (5-14 wt %), and carboxyls (0-4 wt %). Together with the total carbohydrates (23-27 wt %), this approach leads to >90 wt % of the WS material in the bio-oils being quantified. We speculate the larger portion of the difference between the total carbohydrates and hydrolyzable sugars is the missing furanic fraction. Further refinement of the suggested methods and development of separation schemes to obtain and quantify subfractions with homogeneous composition (e.g., carbohydrates, high molecular weight WS phenols, furans, and dehydrated sugars) warrant further investigation.