The unusual green photoluminescence (PL) of N,N-dimethylformamide (DMF)/hydrochloric acid (HCl)/europium chloride (EuCl3) solutions discovered earlier was investigated in more detail to clarify the emission mechanism. It was revealed that the DMF/HCl pair alone can yield a green PL band under UV excitation, and the emission has features of that of excimers. The addition of EuCl3 salt to the solution further stimulates the green emission. The quantum yield of the line emission of Eu3+ ions at 592 and 612 nm is also affected by the presence of HCl in the solution. Both the green emission band and Eu3+ emission lines possess a common channel of excitation at similar to 280 nm. This channel is the only source for the green emission band and an additional source for the Eu3+ emission lines, which can also be stimulated through a conventional Eu3+ excitation channel at 394 nm. The common excitation channel was found to be time-dependent, and its excitation maximum gradually shifts to longer wavelengths. Changes in the PL profiles of europium ions were also observed depending on the presence of HCl and the solution aging.