Resumen: The spontaneous amino-yne click reaction is introduced for the first time as a fast, efficient, and ambient temperature strategy for preparing multi-responsive Liquid Crystal Elastomer (LCE) actuators. This synthetic approach relies on the amino-yne cross-linking between secondary amines along the main chain of poly(β-amino ester) liquid crystal oligomers and a dipropiolate-functionalized cross-linker, rendering β-aminoacrylate cross-linking points. After alignment and locking via dynamic transesterification at 30 °C, the resulting LCE actuators exhibit reversible and reproducible thermal and light-induced actuation. The generated tension and activation kinetics are easily tunable by adjusting the cross-linker content. Additionally, leveraging the acid-triggered reactivity of the network enables it to respond to additional stimuli, including water-driven actuation. By integrating the capability for dynamic bond exchange, this LCE formulation opens new avenues for designing structures with complex molecular orientation patterns. As a proof of concept, a star-shaped soft actuator is fabricated, demonstrating diverse programmable actuation modes. Idioma: Inglés DOI: 10.1002/smll.202509070 Año: 2025 Publicado en: Small (2025), e09070 [11 pp.] ISSN: 1613-6810 Financiación: info:eu-repo/grantAgreement/ES/DGA/E47-23R Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2021-126132NB-I00 Financiación: info:eu-repo/grantAgreement/ES/MICIU/CEX2023-001286-S Tipo y forma: Article (Published version) Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)