To address pressing CO₂ mitigation needs in the power sector, this review provides a pragmatic engineering framework for deploying catalytic CO₂ utilization (CCU) technologies. Synthesizing data from a global portfolio of industrial projects across ten major routes—from e-methanol to molten salt electrolysis—we critically address the operational constraint of excluding hazardous chemical units from power plant sites. We introduce a novel three-tiered deployment framework to resolve this: (A) capture-for-sale to external offtakers, (B) near-plant modular conversion into transportable products, and (C) on-site coupled production of low-hazard materials. Using a unified techno-economic model, we perform a cross-route comparison to identify critical cost drivers and profitability thresholds. Our analysis concludes that a portfolio approach is essential, guided by local resource endowments and market access. This review provides an actionable, data-driven guide for utilities, investors, and policymakers, bridging the gap between catalytic science and bankable, large-scale project deployment.