Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a biodegradable biopolymer from the PHAs family that has potential to replace conventional plastics and reduce plastic pollution. However, PHBV has thermo-sealability issues, making it challenging to use for bags. Blending it with polycaprolactone (PCL) could address this but may alter the barrier properties of the films, affecting their effectiveness as food packaging material. This study examined the properties and heat-sealing capacity of PHBV/PCL blend films (ratios: 60/40, 50/50, and 40/60), obtained by melt blending and compression moulding. Both polymers are immiscible and were in separated phases; the continuous phase was PHBV in the 60/40 blend and PCL in the 40/60 blend, while the 50/50 sample exhibited interpenetrating bicontinuous phases of both polymers. The permeability to water vapour, oxygen, and D-limonene increased as the PCL content rose, especially when it formed the continuous phase in the matrix. The elastic modulus and resistance to break decreased, while extensibility increased, more markedly when PCL was the continuous phase. However, the continuity of PCL phase provided the films with better thermal adhesion and seal strength. The 50/50 blend showed the best balance between heat sealability and barrier properties, making it the most suitable for food packaging in sealed bags.