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The 45°-mirror terminated polymer waveguides fabricated on a silicon substrate are demonstrated for on-chip out-of-plane optical interconnects. The silicon 45° microreflectors are fabricated on an orientation-defined (100) silicon substrate by using anisotropic chemical wet etching. On using a photolithography process, we observe two vertically bending paths at the input and output ports of polymer waveguide on a silicon substrate with 45° microreflectors. The transmission efficiency of -3.77 dB is measured for a 0.5-cm polymer waveguide combined with the 45° microreflectors. The optical loss occurring at the 45°-mirror is -0.27 dB. The channel-to-channel crosstalk for the 250-μm pitch is less than -40 dB. The wider alignment tolerance up to ±15 μm would facilitate the active-device assembly on a silicon substrate.