In living systems,i nterfacial molecular interactions control many biological processes.N ew stimuli-responsive strategies are desired to providev ersatile model systems that can regulate cell behavior in vitro.D escribed here are potential-responsive surfaces that control cell adhesion and release as well as stem cell differentiation. Cell adhesion can be modulated dynamically by applying negative and positive potentials to surfaces functionalized with tailored monolayers. This process alters cell morphology and ultimately controls behavior and the fate of the cells.C ells can be detached from the electrode surface as intact clusters with different geometries using electrochemical potentials.I mportantly,m orphological changes during adhesion guide stem cell differentiation. The higher accessibility of the peptide under ap ositive applied potential causes phenotypic changes in the cells that are hallmarks of osteogenesis,w hereas lower accessibility of the peptide promoted by negative potentials leads to adipogenesis.Biophysical cues play essential roles in regulating cellular behavior in vivo and in vitro. [1,2] Apoptosis, [3] adhesion, [4][5][6][7] proliferation, [6] migration, [8] and differentiation [9][10][11] phenotypes of cells are closely associated with molecular-level biophysical cues created within the extracellular matrix (ECM). Hence,g aining control over the biophysical cues that can influence cellular behavior would facilitate the design of an optimal ECM for controlling cellular processes and defining cell fate.Promoting specific interactions between molecular interfaces and cells has emerged as apromising means to modulate cellular processes.A rg-Gly-Asp (RGD) peptides were the first synthetic molecular structures found to promote cell adhesion. [12] TheRGD sequence is present in alarge number of ECM proteins and represents aprimary recognition site for cell membrane integrin receptors that mediate adhesion to the ECM. Since the discovery of RGD peptides,n umerous materials have been functionalized with these sequences for different biomedical applications. [13] RGD peptides have been immobilized on various substrates,s uch as hydrogels, [14] gold, [15] or glass [16] and these sequences can be modified to either promote or inhibit cell adhesion.To realize dynamic control of cell adhesion onto substrates during cell cultivation, stimuli-controlled switchable RGD surfaces have been developed and rely on the cleavage of the RGD ligands from the surface in response to electrochemical potential, [17,18] light, [19,20] and enzymes. [21] However, this type of cleavage process is irreversible and therefore cannot be used dynamically.I nn ative tissues,c ells exhibit multiple transient interactions with the local ECM, especially during tissue morphogenesis,w ound healing, and cancer progression. [22,23] This need for dynamic control provides arationale for developing more tunable platforms.T here are several strategies for the reversible control of the biophysical properties of ECMs, [24][25][26][27][28]...