Mussel-inspired coatings, known for their outstanding substrate-independent adhesive capabilities, have numerous potential applications in materials science and biomedical fields. To improve the understanding of how these polymers’ molecular structure and chemical composition affect their coating mechanisms and resulting coating properties, we herein developed three mussel-inspired polymers: dendritic polyglycerol with 40% catechol groups and 60% amines (dPG40), linear polyglycerol with 80% catechols and 20% amines (lPG80), and finally lPG40 with 40% catechols and 60% amines. After a series of characterizations, we found that chemical surface modification with a monolayer coating can be easily achieved with MI-lPG40, and that robust and well-defined nano- to micro-structural surface coatings are possible with MI-lPG80 and MI-dPG40. Tunable properties were found to include not only coating speed, but coating thickness, roughness and surficial topography. This diverse suite of controllable attributes enables mussel-inspired polyglycerol (MiPG) coatings to satisfy a wide-range of applications on multiple materials.