Entanglement is a striking feature of quantum mechanics, and it has a key property called unextendibility. In this paper, we present a framework for quantifying and investigating the unextendibility of general bipartite quantum states. First, we define the unextendible entanglement, a family of entanglement measures based on the concept of a state-dependent set of free states. The intuition behind these measures is that the more entangled a bipartite state is, the less entangled each of its individual systems is with a third party. Second, we demonstrate that the unextendible entanglement is an entanglement monotone under two-extendible quantum operations, including local operations and one-way classical communication as a special case. Normalization and faithfulness are two other desirable properties of unextendible entanglement, which we establish here. We further show that the unextendible entanglement provides efficiently computable benchmarks for the rate of exact entanglement or secret key distillation, as well as the overhead of probabilistic entanglement or secret key distillation.