Understanding the size-dependent electronic properties of germanium nanocrystals (Ge NCs) is of fundamental importance for improving the efficiency of optoelectronic devices based on such NCs. Here, Ge NCs with a tunable size were synthesized by magnetron-sputtering cluster-beam deposition, where the size of the as-deposited Ge NCs can be finely controlled between 6 and 36 nm by helium gas flow rates and variable magnetic field configurations above the target surface. Because the size of the as-deposited Ge NCs highly depends on the nucleation process inside the plasma region, a detailed comparison between these two process parameters on the size control was formulated from the perspective of the growth kinetic mechanism. Furthermore, the local surface potential of different-sized Ge NCs deposited on n-type silicon substrates was measured by Kelvin probe force microscopy. The surface potential fluctuation of n-type Si covered by Ge NCs shows a strong size-dependent relationship with the size of the Ge NCs, whereas the surface potential fluctuation increases when their size reduced. Because the surface potential fluctuation between the intrinsic Ge NCs and the n-type silicon substrate tends to get smaller as the NCs' size decreases due to the quantum confinement effect, the number of charges transferred between the electronic bands will reduce as the size of Ge NCs decreases. The latter exactly explains the observed experimental results. Therefore, this work offers a perspective to understand the behavior of charge transfer, which plays an important role in the performance of optoelectronic devices.