On-surface condensation of boronic acids is exploited to synthesize a 2D extended framework1) as well as planar molecules2) on Au(111) surface. Despite exhibiting a vitreous morphology, the boroxine framework shows dispersion of the valence band states; moreover, the boroxine-gold interface presents a hybrid metal-organic electronic orbital, which is able to promote ultra-fast charge transfer2). These aspects make the system a good candidate as electrode in the design of electronic devices. Employed as hosting template, the framework presents a good chemical affinity with amines, thus preserving the Lewis acid character the boroxine has in chemical synthesis processes. We explored the same electronic properties for different boroxine-based molecules synthesized on surface. In this case, we investigated the role of the sample temperature on the synthesis process and we identified a precursor state of the boronic condensation.