Plant cell walls represent an abundant, renewable source of biofuel and other useful products. The major bottleneck for the industrial scale-up of their conversion to simple sugars (saccharification), to be subsequently converted by microorganisms into ethanol or other products, is their recalcitrance to enzymatic saccharification. We investigated whether the structure of pectin that embeds the cellulose-hemicellulose network affects the exposure of cellulose to enzymes and consequently the process of saccharification. Reduction of de-methyl-esterified homogalacturonan (HGA) in Arabidopsis plants through the expression of a fungal polygalacturonase (PG) or an inhibitor of pectin methylesterase (PMEI) increased the efficiency of enzymatic saccharification. The improved enzymatic saccharification efficiency observed in transformed plants could also reduce the need for acid pretreatment. Similar results were obtained in PG-expressing tobacco plants and in PMEI-expressing wheat plants, indicating that reduction of de-methyl-esterified HGA may be used in crop species to facilitate the process of biomass saccharification.biofuel | pectin | plant cell wall | pectin methylesterase inhibitor | polygalacturonase P lant biomass has been a source of energy for most part of human history and, due to the increasing demand for renewable materials and industrial products, is reconsidered today as a possible strategic resource. Plant cell walls comprise a significant proportion of the lignocellulosic biomass (1) and are a potentially abundant substrate for bioconversion to ethanol and other industrial products (2). They are composed of a heterogeneous polysaccharidic matrix associated with components like lignin and proteins. Saccharification, a key process for the production of ethanol, is the degradation of the wall polysaccharides into fermentable sugars. Enzymatic hydrolysis is the most promising and environmentally friendly technology available for saccharification (3, 4), but the recalcitrance of cell walls to hydrolysis is the major bottleneck for the industrial scale-up of this process (2). Thermochemical pretreatments using high temperature, toxic acids, peroxides, and ammonia, often along with some form of mechanical disruption, are currently required to make biomass accessible to cell wall-degrading enzymes and represent up to 30% of the cost of biofuel production (2).Modification of the cell wall structure may be useful for reducing pretreatments and improving the overall saccharification process. For example, it has been shown that reducing the lignin content in transgenic alfalfa plants improves saccharification efficiency, although it can reduce biomass yield (5). A cell wall component that, particularly in dicots, is critical for tissue integrity and accessibility to cell wall-degrading enzymes is the cohesive pectin matrix embedding the cellulose-hemicellulose network, which in turn contains the major strength-conferring elements. It is well known that intermolecular bonds of pectin, mediated by acidic homogalac...