W-structured type-II superlattices (W-SLs) were initially developed to increase the gain of mid-wave infrared (MWIR) lasers. The design addressed the reduced optical transition matrix elements due to the spatial displacement between valence and conduction band wavefunctions in the type-II superlattice (T2SL), and further improved the differential optical gain by providing a mostly two-dimensional density of states. As a result, W-SL and W interband cascade lasers have lower thresholds and higher pulsed and cw operating temperatures than any other III-V interband MWIR lasers. These same features give W-SLs desirable properties for IR detectors, and here we report for the first time on characteristics of W-SLs used for long-wave and very long-wave IR photodiodes. IR transmission measurements of W and conventional T2SL photodiodes revealed absorption characteristics that are well described by theory, including line shape and peak absorption coefficient values which are about a factor of 2 greater in the W-SLs. Similarly, the low temperature photoluminescence shows much higher and sharper emission intensity in the W-SLs. While the W-SLs have demonstrated superior optical properties, as predicted, additional work is needed to achieve higher detector quantum efficiency. Results suggest that the excess carrier collection in the W-structures is reduced with respect to similar T2SL structures, especially for the lowest energy state. Possible mechanisms of excess carrier loss, as well as new designs to improve charge collection, in the W-SL, will be discussed.