Experimental studies on the formation of highly charged ions of medium-Z elements using femtosecond laser pulses with different contrast levels were carried out. Multiply charged Fe ions were generated by laser pulses with 35 fs duration and an intensity exceeding 10²¹ W/cm². Using high-resolution X-ray spectroscopic methods, bulk electron temperature of the generated plasma has been identified. It is shown that the presence of a laser pre-pulse at a contrast level of 10⁵–10⁶ with respect to the main pulse drastically decreases the degree of Fe ionization. We conclude that an effective source of energetic, multiply charged moderate and high-Z ions based on femtosecond laser–plasma interactions can be created only using laser pulses of ultra-high contrast.