Carbon dioxide (CO2) fluxes in regulated Alpine rivers are driven by multiple biogeochemical and anthropogenic processes, acting on different spatiotemporal scales. We quantified the relative importance of these drivers and their effects on the dynamics of CO2 concentration and atmospheric exchange fluxes in a representative Alpine river segment regulated by a cascading hydropower system with diversion, which includes two residual flow reaches and a reach subject to hydropeaking. We combined instantaneous and time-resolved water chemistry and hydraulic measurements at different times of the year, and quantified the main CO2 fluxes by calibrating a one-dimensional transport-reaction model with measured data. As a novelty compared to previous inverse modelling applications, the model also included carbonate buffering, which contributed significantly to the CO2 budget of the case study. The spatiotemporal distribution and drivers of CO2 fluxes depended on hydropower operations. Along the residual flow reaches, CO2 fluxes were directly affected by the upstream dams only in the first ~ 2.5 km, where the supply of supersaturated water from the reservoirs was predominant. Downstream of the hydropower diversion outlets, the CO2 fluxes were dominated by systematic sub-daily fluctuations in CO2 transport and evasion fluxes (`carbopeaking') driven by hydropeaking. Hydropower operational patterns and regulation approaches in Alpine rivers affect CO2 fluxes and their response to biogeochemical drivers significantly across different temporal scales. Our findings highlight the importance of considering all scales of CO2 variations for accurate quantification and understanding of these impacts, to clarify the role of natural and anthropogenic drivers in global carbon cycling.