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Building upon our prior model for self-coacervation [Budkov et al., Soft Matter 19, 3281\u20133289 (2023)], we demonstrate that strong electrostatic dipole\u2013dipole correlations between monomeric units, coupled with attraction to pore walls, can induce capillary-driven liquid\u2013liquid phase separation inside the pore\u2014a phenomenon we term capillary-induced self-coacervation. Using a thermomechanical approach (Budkov et al., J. Stat. Mech.: Theory Exp. 2024, 123201), we calculate the disjoining pressure, revealing a pronounced non-monotonic dependence on pore width linked to coacervate film formation and rupture. Remarkably, we identify a crossover between two film formation mechanisms controlled by wall attraction strength. For weak adsorption, film formation is bridging-dominated, with critical pore width scaling as Hc \u223c N1\/2. For strong adsorption, the system crosses over to a cohesion-dominated regime where Hc saturates to an N-independent plateau, indicating collective phase behavior governed by a confinement-induced shift of the local binodal. This duality reveals the interplay between single-chain connectivity and collective thermodynamics in confined polyzwitterions. The theory offers new insights into coacervate film formation on mineral surfaces, with implications for prebiotic compartmentalization.<\/jats:p>","DOI":"10.1063\/5.0331572","type":"journal-article","created":{"date-parts":[[2026,4,16]],"date-time":"2026-04-16T11:32:10Z","timestamp":1776339130000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":2,"title":["Theory of capillary-induced self-coacervation in zwitterionic polymer solutions"],"prefix":"10.1063","volume":"164","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6949-231X","authenticated-orcid":false,"given":"Nikolai N.","family":"Kalikin","sequence":"first","affiliation":[{"name":"Laboratory of Multiscale Modeling of Molecular Systems, G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences 1 , Akademicheskaya St. 1, 153045 Ivanovo,","place":["Russia"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6757-754X","authenticated-orcid":false,"given":"Petr E.","family":"Brandyshev","sequence":"additional","affiliation":[{"name":"Laboratory of Computational Physics, HSE University 2 , Tallinskaya St. 34, 123458 Moscow,","place":["Russia"]},{"name":"School of Applied Mathematics, HSE University 3 , Tallinskaya St. 34, 123458 Moscow,","place":["Russia"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9061-2745","authenticated-orcid":false,"given":"Yury A.","family":"Budkov","sequence":"additional","affiliation":[{"name":"Laboratory of Multiscale Modeling of Molecular Systems, G.A. 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