It is demonstrated that a combination of microsecond transient photocurrent measurements and film morphology characterization can be used to identify a charge-carrier blocking layer within polymer:fullerene bulk-heterojunction solar cells. Solution-processed molybdenum oxide (s-MoOx) interlayers are used to control the morphology of the bulk-heterojunction. By selecting either a low- or high-temperature annealing (70 degrees C or 150 degrees C) for the s-MoOx layer, a well-performing device is fabricated with an ideally interconnected, high-efficiency morphology, or a device is fabricated in which the fullerene phase segregates near the hole extracting contact preventing efficient charge extraction. By probing the photocurrent dynamics of these two contrasting model systems as a function of excitation voltage and light intensity, the optoelectronic responses of the solar cells are correlated with the vertical phase composition of the polymer:fullerene active layer, which is known from dynamic secondary-ion mass spectroscopy (DSIMS). Numerical simulations are used to verify and understand the experimental results. The result is a method to detect poor morphologies in operating organic solar cells.