Compared to animal proteins, this paper describes the use of plant proteins as alternative emulsifiers in double emulsion (DE) fabrication followed by complex coacervation. This is an additional way to improve stability, sustainability and lower production costs. In this study, kappa-carrageenan (k-carr) was used in complex coacervation with DE stabilised by pea protein isolate (PPI), mung bean protein isolate and chickpea protein concentrate (CPC) at pH 2 and 3 to form microcapsules (DECC). By investigating the particle sizes, microstructures and visual observations over 9 days at 4 °C, PPI/k-carr DECC and CPC/k-carr DECC at pH 2 were the most stable. Riboflavin encapsulation in PPI/k-carr DECC achieved an encapsulation efficiency of 65.46%, preserving ~20% of riboflavin across the storage period. As compared to DE systems, complex coacervation significantly improved riboflavin encapsulation stability. The results highlight the potential of PPI as an alternative emulsifier in DECC for the delivery of bioactive compounds.