Electrochemical synthesis in molten salts offers a scalable, cost-effective, and environmentally sustainable method for producing carbon nanomaterials such as graphene and multi-walled carbon nanotubes (MWCNTs). This review presents recent advances in the controlled synthesis and structural characterization of CNTs and graphene via molten salt electrolysis, with emphasis on the relationship between process parameters and material structure. MWCNTs were synthesized using both stationary and pulsed current regimes, where variables such as voltage, current density, temperature, and electrode configuration were optimized to tailor morphological features. Structural analysis included determination of wall number, inner/outer diameters, and chiral indices (m, n), the latter determined via Raman spectroscopy and computational modeling in Python and Mathematica. Further evaluation through topological graph theory using distance-based indices (e.g., Wiener, Balaban) confirms structure-property correlations. Graphene was synthesized electrochemically as a clean alternative to conventional methods. Layer number and distribution were determined using X-ray diffraction (XRD) data, applying both the Scherrer equation and an enhanced model based on Laue functions. This model accurately quantified multilayer configurations, particularly in asymmetric 0 0 2 peaks, by incorporating symmetry metrics and a corresponding algorithm. Finally, interpretable machine learning techniques, specifically decision tree models, were applied to experimental datasets to identify key parameters governing material quality. These models enabled the derivation of empirical rules for optimizing synthesis conditions in both CNT and graphene production. The integration of electrochemical synthesis, structural analysis, and AI-driven modeling provides a robust platform for advancing the sustainable and rational design of carbon nanomaterials in green nanotechnology.