Using new spectroscopic observations obtained as part of the VIMOS Ultra-Deep Survey (VUDS), we performed a systematic search for overdense environments in the early universe (z> 2) and report here on the discovery of Cl J0227-0421, a massive protocluster at z = 3.29. This protocluster is characterized by both the large overdensity of spectroscopically confirmed members, δgal = 10.5 ± 2.8, and a significant overdensity in photometric redshift members. The halo mass of this protocluster is estimated by a variety of methods to be ~3 × 1014ℳ⊙ at z ~ 3.3, which, evolved to z = 0 results in a halo mass rivaling or exceeding that of the Coma cluster. The properties of 19 spectroscopically confirmed member galaxies are compared with a large sample of VUDS/VVDS galaxies in lower density field environments at similar redshifts. We find tentative evidence for an excess of redder, brighter, and more massive galaxies within the confines of the protocluster relative to the field population, which suggests that we may be observing the beginning ofenvironmentally induced quenching. The properties of these galaxies are investigated, including a discussion of the brightest protocluster galaxy, which appears to be undergoing vigorous coeval nuclear and starburst activity. The remaining member galaxies appear to have characteristics that are largely similar to the field population. Though we find weaker evidence of the suppression of the median star formation rates among and differences in the stacked spectra of member galaxies with respect to the field, we defer any conclusions about these trends to future work with the ensemble of protostructures that are found in the full VUDS sample.