The construction of a protocell with dynamic hierarchical structures via spontaneous phase separation sheds light on the mechanisms of life processes. Taking advantage of the transition from the liquid to solid phase, we built composite droplets with PLL/oligo/oligocomp solid particles randomly distributed inside a PLL/oligo liquid coacervate. The circulation and vacuolization under an electric field drive the particles into a fibrous structure and even clusters. A PLL/oligo/oligocomp solid phase can also form on the interface of the PLL/oligo coacervate, turning the droplet into a vesicular structure.