Biorefining of lignocellulosic biomass to fuels/chemicals has recently gained immense research momentum. Current study reports sequential pretreatment of sunflower stalk (SFS) biomass in a combinatorial regime involving alkali (NaOH) and ionic liquid 1-butyl-3-methyl imidazolium chloride. The pretreatment enhanced the enzymatic digestibility, and resulted in increased sugar yield (163.42 mg/g biomass) as compared to standalone pretreatment using alkali (97.38 mg/g biomass) or ionic liquid (79.6 mg/g biomass). Ultrastructural and morphological analysis (FTIR and SEM) of pretreated biomass showed that the combined ionic liquid and alkali pretreatment causes more drastic alterations in the biomass ultrastructure as compared to alone ionic liquid or alkali pretreatment. Thus, combined pretreatment led to ease of enzymatic saccharification and consequent increased sugar yield, and this observation was corroborated by physicochemical analysis of the pretreated biomass. The pretreated SFS biomass was subjected to consolidated bioprocessing for its direct conversion to bioethanol in a single vessel.