A rigorous probabilistic construction of Liouville conformal field theory (LCFT) on the Riemann sphere was recently given by David-Kupiainen and the last two authors. In this paper, we focus on the connection between LCFT and the classical Liouville field theory via the semiclassical approach. LCFT depends on a parameter $\gamma \in (0,2)$ and the limit $\gamma \to 0$ corresponds to the semiclassical limit of the theory. Within this asymptotic and under a negative curvature condition (on the limiting metric of the theory), we determine the limit of the correlation functions and of the associated Liouville field. We also establish a large deviation result for the Liouville field: as expected, the large deviation functional is the classical Liouville action. As a corollary, we give a new (probabilistic) proof of the Takhtajan-Zograf theorem which relates the classical Liouville action (taken at its minimum) to Poincar\'e's accessory parameters. Finally, we gather conjectures in the positive curvature case (including the study of the so-called quantum spheres introduced by Duplantier-Miller-Sheffield).