Tetrapod-shaped CdSe nanocrystals were obtained using a simple method. HRTEM shows that the average size of the tetrapod core are about 4 nm, widths of the tetrapod arms are about 4 nm and lengths of the arms are about 20 nm. XRD patterns reveal that the OA-capped CdSe tetrapod nanocrystals have a hexagonal wurtzite structure. A hybrid solar cell fabricated based on an 8:1 (w/w) blend of CdSe tetrapod nanocrystals and MEH–PPV showed a maximum power conversion efficiency of 0·46% under an air mass 1·5 global condition. The effects of nanocrystal composition on the photovoltaic properties of hybrid solar cells based on nanotetrapods CdSe/MEH–PPV were investigated. The power conversion efficiency values initially increased and then decreased, but the V OC values linearly decreased from 1·1 to 0·25 V with increased CdSe nanotetrapod in the blend film. The significant quenching of PL with increased nanotetrapod concentration indicated photo-induced charge transfer between MEH–PPV and CdSe.