Bio-oils
obtained from lignocellulosic biomass pyrolysis are promising
energetic resources. However, their high oxygen content is responsible
for storage and corrosion issues and does not allow their direct use
as biofuels. Therefore, upgrading treatments are necessary to reduce
the oxygen content and to give them physiochemical properties close
to those of fossil fuels. To monitor the efficiency of both conversion
and upgrading processes, the extensive molecular composition of bio-oil
is needed. In that sense, two approaches can be applied for bio-oil
characterization. The non-targeted one, using high-resolution mass
spectrometry, ensures to distinguish and assign tens of thousands
features at the isobaric level. On the other hand, targeted analyses,
especially with chromatography hyphenated to mass spectrometry, allow
quantifying and obtaining isomeric information on the bio-oil species.
In this review, both approaches will be discussed through the different
studies performed in that field. Particular interest will be given
to heavy compounds analysis by Fourier transform mass spectrometry
(FTMS) and liquid and supercritical fluid chromatographies. Most of
the analyses are performed either by FTMS or by chromatography. Only
a limited number of works report bio-oil characterization by liquid
chromatography hyphenated to FTMS. These hyphenated methods are complementary
and ensured to highlight hitherto unknown bio-oil species. It therefore
represents the next step for deciphering the complex molecular composition
of bio-oil.