The unambiguous detection and quantification of entanglement is a hot topic of scientific research, though it is limited to low dimensions or specific classes of states. Here we identify an additional class of quantum states, for which bipartite entanglement measures can be efficiently computed, providing new rigorous results. Such states are written in arbitrary $d\times d$ dimensions, where each basis state in the subsystem A is paired with only one state in B. This new class, that we refer to as pair basis states, is remarkably relevant in many physical situations, including quantum optics. We find that negativity is a necessary and sufficient measure of entanglement for mixtures of states written in the same pair basis. We also provide analytical expressions for a tight lower-bound estimation of the entanglement of formation, a central quantity in quantum information.