We present a large-scale galaxy structure Cl J021734-0513 at z~0.65 discovered in the UKIDSS UDS field, made of ~20 galaxy groups and clusters, spreading over 10Mpc. We report on a VLT/VIMOS spectroscopic follow-up program that, combined with past spectroscopy, allowed us to confirm four galaxy clusters (M_200_~10^14^M_{sun}_) and a dozen associated groups and star-forming galaxy overdensities. Two additional filamentary structures at z~0.62 and 0.69 and foreground and background clusters at 0.6<z<0.7 were also confirmed along the line of sight. The structure subcomponents are at different formation stages. The clusters have a core dominated by passive galaxies and an established red sequence. The remaining structures are a mix of star-forming galaxy overdensities and forming groups. The presence of quiescent galaxies in the core of the latter shows that 'pre-processing' has already happened before the groups fall into their more massive neighbours. Our spectroscopy allows us to derive spectral index measurements e.g. emission/absorption line equivalent widths, strength of the 4000{AA} break, valuable to investigate the star formation history of structure members. Based on these line measurements, we select a population of 'post-starburst' galaxies. These galaxies are preferentially found within the virial radius of clusters, supporting a scenario in which their recent quenching could be prompted by gas stripping by the dense intracluster medium. We derive stellar age estimates using Markov Chain Monte Carlo-based spectral fitting for quiescent galaxies and find a correlation between ages and colours/stellar masses which favours a top-down formation scenario of the red sequence. A catalogue of ~650 redshifts in UDS is released alongside the paper (via MNRAS online data).