Several types of silicon‐based inverse‐opal films are synthesized, characterized by a range of experimental techniques, and studied in terms of electrochemical performance. Amorphous silicon inverse opals are fabricated via chemical vapor deposition. Galvanostatic cycling demonstrates that these materials possess high capacities and reasonable capacity retentions. Amorphous silicon inverse opals perform unsatisfactorily at high rates due to the low conductivity of silicon. The conductivity of silicon inverse opals can be improved by their crystallization. Nanocrystalline silicon inverse opals demonstrate much better rate capabilities but the capacities fade to zero after several cycles. Silicon–carbon composite inverse‐opal materials are synthesized by depositing a thin layer of carbon via pyrolysis of a sucrose‐based precursor onto the silicon inverse opals. The amount of carbon deposited proves to be insufficient to stabilize the structures and silicon–carbon composites demonstrate unsatisfactory electrochemical behavior. Carbon inverse opals are coated with amorphous silicon producing another type of macroporous composite. These electrodes demonstrate significant improvement both in capacity retentions and in rate capabilities. The inner carbon matrix not only increases the material conductivity but also results in lower silicon pulverization during cycling.