Self-assembled monolayers (SAMs) of n-dodecanethiol (CHSH) and n-dodecaneselenol (CHSeH) on polycrystalline copper have been elaborated with the purpose of achieving densely packed and crystalline-like assemblies. By combining the surface sensitivity of polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), the effect of the self-assembly time (15 min, 30 min, 1 h, 2 h and 24 h) on the formation of n-dodecanethiol and n-dodecaneselenol monolayers on untreated and electrochemically reduced polycrystalline copper has been investigated. On electrochemically reduced copper, PM-IRRAS spectroscopy shows that both molecules are able to form well organized layers. SFG spectroscopy indicates that the CHSeH SAMs are slightly better ordered than those achieved with CHSH. On untreated copper, the two molecules lead to different film organizations. Both PM-IRRAS and SFG indicate that CHSH SAMs are of the same film quality as those obtained on electrochemically reduced copper. On the contrary, CHSeH monolayers are invariably poorly organized at the molecular level.