The charge separation and transport dynamics in CdSe nanoparticle:poly(3‐hexylthiophene) (P3HT) blends are reported as a function of the shape of the CdSe‐nanoparticle electron acceptor (dot, rod, and tetrapod). For optimization of organic photovoltaic device performance it is crucial to understand the role of various nanostructures in the generation and transport of charge carriers. The sample processing conditions are carefully controlled to eliminate any processing‐related effects on the carrier generation and on device performance with the aim of keeping the conjugated polymer phase constant and only varying the shape of the inorganic nanoparticle acceptor phase. The electrodeless, flash photolysis time‐resolved microwave conductivity (FP‐TRMC) technique is used and the results are compared to the efficiency of photovoltaic devices that incorporate the same active layer. It is observed that in nanorods and tetrapods blended with P3HT, the high aspect ratios provide a pathway for the electrons to move away from the dissociation site even in the absence of an applied electric field, resulting in enhanced carrier lifetimes that correlate to increased efficiencies in devices. The processing conditions that yield optimum performance in high aspect ratio CdSe nanoparticles blended with P3HT result in poorly performing quantum dot CdSe:P3HT devices, indicating that the latter devices are inherently limited by the absence of the dimensionality that allows for efficient, prolonged charge separation at the polymer:CdSe interface. The charge generation and decay dynamics in CdSe nanoparticle blends with P3HT is studied with time‐resolved microwave conductivity as a function of CdSe nanoparticle shape and is correlated with photovoltaic device performance. An enhanced carrier lifetime observed for high aspect ratio nanoparticles (nanorods and tetrapods) explains the better photovoltaic performance of these devices compared to those of quantum dot devices.