An expeditious green method for the synthesis of diverse valued substituted pyrroles through a Paal–Knorr condensation reaction, using a variety of amines and 2,5-hexanedione/2,5-dimethoxytetrahydrofuran in the presence of a low melting mixture of N,N’-dimethylurea and L-(+)-tartaric acid (which acts as a dual catalyst/solvent system), has fruitfully been revealed. Herein, we have disclosed the applicability of this simple yet effective strategy for the generation of mono- and dipyrroles in good to excellent yields. Moreover, C₃-symmetric tripyrrolo–truxene derivatives have also been assembled by means of cyclotrimerization, Paal–Knorr and Clauson–Kaas reactions as crucial steps. Interestingly, the melting mixture was recovered and reused with only a gradual decrease in the catalytic activity (over four cycles) without any significant drop in the yield of the product. This particular methodology is simple, rapid, environmental friendly, and high yielding for the generation of a variety of pyrroles. To the best of our knowledge, the present work reveals the fastest greener method reported up to this date for the construction of substituted pyrroles by utilizing the Paal–Knorr synthetic protocol, achieving impressive yields under operationally simple reaction conditions without involving any precarious/dangerous catalysts or unsafe volatile organic solvents.