Grape seeds were deconstructed in both hydrothermal and supercritical ethanol media with a combination of two metal chlorides (TiCl4:MgCl2) to produce bio-oils. The use of metal chloride additives in supercritical ethanol achieved the highest bio-oil yield of 49.2 wt% (300 degrees C, 30 min). Both the hydrothermal and supercritical ethanol deconstruction with the additives (TiCl4:MgCl2 = 4 mmol:4mmol) produced the bio-oils with a higher heating value (HHV) of 35 MJ/Kg. Gas chromatography-mass spectrometry (GC-MS) analysis of the bio-oils showed that the major products in bio-oils from the hydrothermal deconstruction were acids while the majority products in bio-oils form the supercritical ethanol deconstruction were esters. Nuclear magnetic resonance (NMR) data of the bio-oils suggested that both hydrothermal and supercritical ethanol deconstruction with metal chlorides significantly reduced the non-condensed OH and oxygenated lignin sub-units in bio-oils; while only supercritical ethanol deconstruction with metal chlorides reduced the aliphatic OH and O-alkylated structures in bio-oils.