Here, we present the production method of 4,4 '-trimethylenebi(sulfo)pyridinium tetrachloroaluminate (TMBSPTCA) organic-inorganic hybrid salt as an eco-friendly, acidic-basic heterogeneous catalyst for the synthesis of benzo[a]pyrano[2,3-c]phenazine via one-pot solvent-free multicomponent domino reaction of 2hydroxynaphthalene-1,4-dione (1 mmol), benzene-1,2-diamine (1 mmol), malononitrile (1 mmol), and aromatic aldehydes (1 mmol) by generating C-C, C--C, C-O, C-N and C--N bonds. The XRD (X-ray diffraction), FT-IR (Fourier-transform infrared spectroscopy), 13C NMR, 1H NMR, Mass, TGA (thermal gravimetric analysis), FE-SEM (field emission scanning electron microscopy), and EDX (energy dispersive spectrometer), Ultraviolet-visible (UV-Vis) spectroscopy approved the framework of this hybrid salt. The structural results revealed that the catalyst is in the form of interconnected quasi-spherical clusters with a size of 50-150 nm with a dominant crystalline nature. Good thermal stability up to 600 degrees C, high purity, and its remarkable acidic property with a Hammett acidity function (H0) of 1.42 are other features of the synthesized hydride salt. Eye-catching optimal conditions (60 degrees C, solvent-free, and 8 mol % TMBSPTCA) compared to previous protocols, rapid production of derivatives 1a-13a in a short time with excellent yields (7 to14 min, 92 to 98 %), reasonable values of turnover number (TON: 11.50 to 12.25) and turnover frequency (TOF: 0.82 to 1.75 min-1), the performance of the catalyst in the role of an acid-base duel with sulfonic acid and tetrachloroaluminate active centers, and the ability to easily recycle the catalyst (5 times) are the prominent advantages of this work.