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The originally synthesized hydrophobic hybrid polymer Bu₄N⁺-POM-PS is tuned into a giant amphiphile composed of a hydrophilic H⁺-POM head and a hydrophobic PS tail through protonation. Immediately, the hybrid amphiphiles self-assemble into vesicles. A further annealing treatment induces an evolution from vesicles to tubular aggregates containing H⁺-POM nanotubes wrapped with PS coronas. After this transformation, the tubular aggregates grow further and then arrange in a parallel manner to form domains. This interesting morphology evolution provides us an opportunity to understand the intriguing aggregation behavior of the hybrid amphiphiles and, meanwhile, to generate POM nanotubes which might be utilized to create nanomaterials for potential applications.