We study the multi-modal Laplace approximation, given by a weighted Gaussian mixture centred at the local minima of the negative log-density, for sampling from probability measures that concentrate around finitely many modes as an inverse-temperature parameter $n$ grows. Such distributions occur in Bayesian inference in the small noise or large data regime. We derive explicit, non-asymptotic bounds on the Hellinger distance between the multi-modal Laplace approximation and the concentrating posterior. The bound decays like $n^{-1/2}$ with $n$ and the constants depend only polynomially on the dimension $d$. Moreover, we analyse the Laplace mixture as a proposal distribution for self-normalised importance sampling and independent Metropolis--Hastings (IMH) targeting concentration multimodal distributions. We derive asymptotic results, as $n\to\infty$, on the effective sample size in case of importance sampling as well as on the average acceptance probability, lag-one autocorrelation, and spectral gap in case of IMH. Numerical experiments illustrate and verify our theoretical findings.

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