In this study, pyrolysis of residual biomass from the agro-alimentary industry of Argentina was investigated. The studied biomasses were rice husk, peanut shell and wheat straw. The effect of pyrolysis temperature over solid (bio-char), liquid (bio-oil) and gas (bio-gas) fractions weight yields were evaluated for each biomass, in the range of 350-650 °C. The maximum yield of bio-oil was obtained at 550 °C for rice husk (45 wt%) and wheat straw (58 wt%), and at 500 °C for peanut shells (51 wt%). At those temperatures, the data recorded the smallest spread around the mean. Different characterization techniques of raw biomass were reported, namely, thermal behavior; proximate and ultimate analysis; content of Ca, Al, K, Si and Fe; and hemicellulose, cellulose and lignin composition. Bio-oils characterization included water content and chemical compounds identification. Furthermore, bio-char HHV and BET surface area were measured. Rice husk bio-oil showed 21% selectivity towards furans of which 75% corresponded to furfural and 5-HMF. Peanut shell bio-char presented the highest Higher Heating Value (7250 kcal/kg) and BET surface area (215 m2/g). In addition, co-pyrolysis reactions and the synergistic effects over obtained products completed this study. Co-pyrolysis bio-oils yields varied between 41 and 46 wt%, for all the mixtures. Bio-oil water content decreased up to 15% for rice husk mixed with peanut shell or wheat straw. Moreover, 5-HMF was detected in all bio-oils, and furfural selectivity was higher than 5% in the three mixtures investigated.