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We study the existence and uniqueness of solutions for coupled Langevin differential equations of fractional order with multipoint boundary conditions involving generalized Liouville–Caputo fractional derivatives. Furthermore, we discuss Ulam–Hyers stability in the context of the problem at hand. The results are shown with examples. Results are asymmetric when a generalized Liouville–Caputo fractional derivative <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mo>(</mo><mi>ρ</mi><mo>)</mo></mrow></semantics></math></inline-formula> parameter is changed.