The definitive role of the intermediate 5,6-dihydroxyindole (DHI) in the formation of polydopamine (PDA) coatings from aqueous dopamine (DA) has not been clearly elucidated and remains highly controversial. Our foray into this debate as reported in this study agrees with some reported assertions that DHI-based coatings are not synonymous with PDA coatings. Our conclusion arises from a systematic comparison of the components and properties of DHI-based coatings and PDA coatings. In addition, through careful copolymerization studies of DA and DHI, our studies reported herein unequivocally suggest that both DA and DHI are partial building blocks for PDA formation. Our results also provide additional evidence of the critical role of DHI in controlling the thickness of PDA coatings, through competitive events between PDA aggregation in solutions and deposition onto substrates. These findings highlight the complex DHI and uncyclized DA moieties interplay between both in the formation of adhesive catechol/amine materials.