Cistus ladanifer L. and Erica arborea L. are the two most representative shrub species from the Iberian Peninsula. With a view to their valorization, their biomass hydrolysate components, obtained from microwave-assisted treatments with choline chloride/urea - HNO3 10%, N,N-dimethylacetamide/NaHCO3 and N,N-dimethylacetamide/CH3OK as solvents, have been measured using a spectrophotometric method. Concentrations of furfural and 5-(hydroxymethyl)furfural (5-HMF) in the filtrate have been determined after reduction with NaBH4. The production of total sugars, reducing sugars and non-reducing sugars has also been assessed. The obtained results support the choice of microwave-assisted choline chloride/urea deep eutectic solvent in acid media as the preferred method (over the polar aprotic solvent-based alternatives) for the extraction of lignin, furfural, 5-HMF and sugars from C. ladanifer and E. arborea biomass, attaining the best production yields for 60 min exposure times. Another is the case if the aim of the treatments is to recovery sugars from both shrubs for subsequent enzymatic saccharification: the very low 5-HMF contents resulting from the dimetylacetamide systems (especially is association with CH3OK) make them highly advantageous as compared to the traditional method using NaOH.