Molecules are fascinating candidates for constructing tunable and electrically conducting devices by the assembly of either a single molecule or an ensemble of molecules between two electrical contacts followed by current‐voltage (I‐V) analysis, which is often termed “molecular electronics”. Recently, there has been also an upsurge of interest in spin‐based electronics or spintronics across the molecules, which offer additional scope to create ultrafast responsive devices with less power consumption and lower heat generation using the intrinsic spin property rather than electronic charge. Researchers have been exploring this idea of utilizing organic molecules, organometallics, coordination complexes, polymers, and biomolecules (proteins, enzymes, oligopeptides, DNA) in integrating molecular electronics and spintronics devices. Although several methods exist to prepare molecular thin‐films on suitable electrodes, the electrochemical potential‐driven technique has emerged as highly efficient. In this Review we describe recent advances in the electrochemical potential driven growth of nanometric various molecular films on technologically relevant substrates, including non‐magnetic and magnetic electrodes to investigate the stimuli‐responsive charge and spin transport phenomena.