α-(Yb1-xErx)2Si2O7 thin films on Si substrates were synthesized by magnetron co-sputtering. The optical emission from Er3+ ions has been extensively investigated, evidencing the very efficient role of Yb-Er coupling. The energy-transfer coefficient was evaluated for an extended range of Er content (between 0.2 and 16.5 at.%) reaching a maximum value of 2 × 10⁻¹⁶ cm⁻³s⁻¹. The highest photoluminescence emission at 1535 nm is obtained as a result of the best compromise between the number of Yb donors (16.4 at.%) and Er acceptors (1.6 at.%), for which a high population of the first excited state is reached. These results are very promising for the realization of 1.54 μm optical amplifiers on a Si platform.