A new theoretical method to study super-multiperiod superlattices has been developed. The method combines the precision of the 8-band kp-method with the flexibility of the shooting method and the Monte Carlo approach. This method was applied to examine the finest quality samples of super-multiperiod Al_0.3Ga_0.7As/GaAs superlattices grown by molecular beam epitaxy. The express photoreflectance spectroscopy method was utilized to validate the proposed theoretical method. For the first time, the accurate theoretical analysis of the energy band diagram of super-multiperiod superlattices with experimental verification has been conducted. The proposed approach highly accurately determines transition peak positions and enables the calculation of the energy band diagram, transition energies, relaxation rates, and gain estimation. It has achieved a remarkably low 5% error compared to the commonly used method, which typically results in a 25% error, and allowed to recover the superlattice parameters. The retrieved intrinsic parameters of the samples aligned with XRD data and growth parameters. The proposed method also accurately predicted the escape of the second energy level for quantum well thicknesses less than 5 nm, as was observed in photoreflectance experiments. The new designs of THz light-emitting devices operating at room temperature were suggested by the developed method.