A　new　gemini　surfactant　with　a　long　and　rigid　spacer,　O,O′-bis(sodium　2-dodecylcarboxylate)-p-dibenzenediol　(referred　to　as　C12φ　2C12),　has　been　synthesized.　Its　aggregation　in　aqueous　solution　has　been　studied　using　static　and　dynamic　light　scattering　measurements.　The　homologue　O,O′-bis(sodium　2-dodecylcarboxylate)-p-　benzenediol　(C12φC12)　whose　spacer　only　contains　a　single　phenyl　group　was　also　examined　for　comparison.　Dynamic　light　scattering　(DLS)　revealed　the　unexpected　existence　of　large　aggregates　in　the　solution　of　C12φ2C12.　However,　C12φ　C12　showed　rather　normal　aggregation　behavior.　Both　the　results　of　intrinsic　viscosity　and　light　scattering　demonstrated　a　loose　structure　for　the　large　aggregates　of　C12φ2C12.　This　behavior　was　attributed　to　an　extending　configuration　of　C12φ　2C12　with　the　two　alkyl　tails　stretching　toward　the　solution　due　to　the　rigidity　of　the　long　spacer.　The　large　network-like　aggregate　formation　was　an　inevitable　outcome　of　spontaneously　reducing　the　energy　of　the　system.　Freeze-fracture　transmission　electron　microscopy　(FF-TEM)　images　and　1H　NMR　measurements　supported　this　speculation.　Due　to　the　columnar-like　molecular　geometry,　the　large　network-like　aggregates　were　directly　transformed　into　rodlike　micelles　with　increasing　surfactant　concentration.　Depending　on　further　micellar　growth,　the　wormlike　micelles　were　finally　formed　as　confirmed　by　rheological　measurements.　©　2012　American　Chemical　Society.