Renewable energy has made significant strides, with the cost of clean electricity plummeting, making the use of renewable electricity for electrocatalytic CO2 reduction to synthesize high-value chemicals and fuels more economically attractive. Notably, certain non-copper-based electrocatalysts have shown remarkable selectivity for C2+ products at low overpotentials, even enabling the production of multi-carbon molecules that are undetectable on copper-based electrodes. This breakthrough opens up new avenues for research into non-copper catalysts. This article offers a thorough review of the latest research progress in employing non-copper-based catalysts for CO2 conversion, focusing on the generation of C2+ products in aqueous media. It explores the complex mechanisms of carbon-carbon coupling and provides a critical assessment of future directions for improving catalyst design, modulating interface microenvironments, and optimizing reaction systems for non-copper-based catalysts in CO2 reduction reactions (CO2RR).