A green and simple approach was developed for the regioselective synthesis of structurally diverse chromenopyrrole frameworks from 3-formylchromones, active methylenes, and α-azido ketones using piperidine as a catalyst in the aqueous medium through a tandem one-pot multicomponent reaction. Further, the synthesized pyrrole framework was successfully converted into biologically significant 6-azaindole derivatives in a simple synthetic transformation. An exciting feature of this synthetic protocol is that the reaction mechanism and formation of the products depend on the nature of the active methylene used. This approach has several advantages such as a transition-metal-free catalyst, a short reaction time, easy separation, an excellent yield, practically simple execution, high regioselectivity, very good atom economy, low E-factor, and no requirement of toxic solvents and chromatographic purification.