We report the serendipitous discovery of a dust-obscured galaxy observed as part of the Atacama Large Millimeter Array (ALMA) Large Program to INvestigate [C II] at Early times (ALPINE). While this galaxy is detected both in line and continuum emissions in ALMA Band 7, it is completely dark in the observed optical/near-infrared bands and only shows a significant detection in the UltraVISTA K-s band. We discuss the nature of the observed ALMA line, that is [C II] at z similar to 4.6 or high-J CO transitions at z similar to 2.2. In the first case, we find a [C II]/FIR luminosity ratio of log(L-[C II]/L-FIR) similar to -2.5, consistent with the average value for local star-forming galaxies (SFGs). In the second case instead, the source would lie at larger CO luminosities than those expected for local SFGs and high-z submillimetre galaxies. At both redshifts, we derive the star formation rate (SFR) from the ALMA continuum and the physical parameters of the galaxy, such as the stellar mass (M-*), by fitting its spectral energy distribution. Exploiting the results of this work, we believe that our source is a 'main-sequence', dusty SFG at z = 4.6 (i.e. [C II] emitter) with log(SFR/M-circle dot yr(-1)) similar to 1.4 and log(M-*/M-circle dot) similar to 9.9. As a support to this scenario our galaxy, if at this redshift, lies in a massive protocluster recently discovered at z similar to 4.57, at only similar to 1 proper Mpc from its centre. This work underlines the crucial role of the ALPINE survey in making a census of this class of objects, in order to unveil their contribution to the global SFR density at the end of the Reionization epoch.