Understanding the relationship between the heterogeneous structure of complex networks and cooperative phenomena occurring on them remains a key problem in network science. Mean-field theories of spin models on networks constitute a fundamental tool to tackle this problem and a cornerstone of statistical physics, with an impressive number of applications in condensed matter, biology, and computer science. In this work we derive the mean-field equations for the equilibrium behavior of vector spin models on high-connectivity random networks with an arbitrary degree distribution and with randomly weighted links. We demonstrate that the high-connectivity limit of spin models on networks is not universal in that it depends on the full degree distribution. Such nonuniversal behavior is akin to a remarkable mechanism that leads to the breakdown of the central limit theorem when applied to the distribution of effective local fields. Traditional mean-field theories on fully-connected models, such as the Curie-Weiss, the Kuramoto, and the Sherrington-Kirkpatrick model, are only valid if the network degree distribution is highly concentrated around its mean degree. We obtain a series of results that highlight the importance of degree fluctuations to the phase diagram of mean-field spin models by focusing on the Kuramoto model of synchronization and on the Sherrington-Kirkpatrick model of spin-glasses. Numerical simulations corroborate our theoretical findings and provide compelling evidence that the present mean-field theory describes an intermediate regime of connectivity, in which the average degree $c$ scales as a power $c \propto N^{b}$ ($b < 1$) of the total number $N \gg 1$ of spins. Our findings put forward a novel class of spin models that incorporate the effects of degree fluctuations and, at the same time, are amenable to exact analytic solutions.