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The authors study the existence of singular radial solutions of the following boundary value problem for the Liouville system NEWLINE\\[NEWLINE-\\Delta u=\\lambda e^v,\\quad -\\Delta v=\\mu e^u,\\quad u=v=0\\text{ on }\\partial B,\\tag{1}NEWLINE\\]NEWLINE as well as the multiplicity of regular solutions.NEWLINENEWLINEIn the first main result, the authors prove that if \\(u,v\\in C^2(B\\setminus \\{0\\})\\) are radial positive solutions of the system \\(-\\Delta u=\\lambda e^v\\), \\(-\\Delta v=\\mu e^u\\), in \\(B\\setminus\\{0\\}\\), then either both \\(u\\) and \\(v\\) admit a smooth extension to \\(B\\) or \\(u\\) and \\(v\\) are both singular and have a \\(\\log\\)-type singularity.NEWLINENEWLINEIn the second main result, the authors prove the existence of singular radial solutions. In particular, they prove that there exists a smooth decreasing function \\(\\bar{h}:]0,+\\infty[\\rightarrow ]0,+\\infty[\\), with \\(\\lim_{\\mu\\rightarrow 0}\\bar{h}(\\mu)=+\\infty\\), \\(\\lim_{\\mu\\rightarrow +\\infty}\\bar{h}(\\mu)=0\\) such that problem (1) has a radial singular solution \\((u,v)\\) if and only if \\(\\lambda=\\bar{h}(\\mu)\\). Moreover, it is proved that the radial singular solution is unique.NEWLINENEWLINEFinally, if the dimension \\(N\\) is not greater than \\(9\\), the authors establish a multiplicity result for regular solutions to problem (1). In particular, they prove that, if \\((\\lambda,\\mu)\\) approaches a fixed point \\((\\mu_0,h(\\mu_0))\\), then the number of regular solutions tends to infinity. 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