This article analyses how capacity building programmes interact with structural constraints in mission-oriented climate policy, focusing on the Italian pilot Let’sGOv (GOverning the Transition through Pilot Actions) within the EU Mission “100 Climate-Neutral and Smart Cities by 2030”. Using an iterative, reflexive methodology (document analysis, participant observation, and qualitative analysis of questionnaires, workshop outputs, and online training feedback), it examines how municipal actors experience and reinterpret capacity building across three coupled dimensions: internal organisational capacity, external stakeholder relations, and multilevel governance interfaces. The empirical setting is a network of nine Italian Mission Cities (Bergamo, Bologna, Florence, Milan, Padua, Parma, Prato, Rome, Turin) supported by technical partners. The bench-learning pathway combined barriers diagnosis, an intensive in-person workshop, and a codesigned online curriculum structured around three thematic clusters (engagement, data, climate finance). Findings indicate that persistent barriers - departmental silos, resource and time scarcity, rigid HR and procurement routines, asymmetric data access, and regulatory instability - are not removed by capacity building; rather, they are progressively articulated, specified, and reframed into actionable organisational and policy demands. Bench-learning strengthens diagnostic and relational capacities and enables modest institutional innovations (templates, protocols, internal task forces, shared policy briefs), while “hard” governance infrastructures largely remain unchanged. The paper argues that networked capacity building contributes to an emerging national climate governance architecture only when it supports collective negotiation with national actors and translates local experimentation into durable multilevel interfaces, mitigating risks of projectification and downward responsibility shifting.