Time-of-flight (TOF) measurements typically require a sample thickness of several micrometers for determining the carrier mobility, thus rendering the applicability inefficient and unreliable because the sample thicknesses are orders of magnitude higher than those in real optoelectronic devices. Here, we use subphthalocyanine (SubPc):C70 as a charge-generation layer (CGL) in the TOF measurement and a commonly hole-transporting layer, N,N'-diphenyl-N,N'-bis(1,1'-biphenyl)-4,4'-diamine (NPB), as a standard material under test. When the NPB thickness is reduced from 2 to 0.3 μm and with a thin 10-nm CGL, the hole transient signal still shows non-dispersive properties under various applied fields, and thus the hole mobility is determined accordingly. Only 1-μm NPB is required for determining the electron mobility by using the proposed CGL. Both the thicknesses are the thinnest value reported to data. In addition, the flexibility of fabrication process of small molecules can deposit the proposed CGL underneath and atop the material under test. Therefore, this technique is applicable to small-molecule and polymeric materials. We also propose a new approach to design the TOF sample using an optical simulation. These results strongly demonstrate that the proposed technique is valuable tool in determining the carrier mobility and may spur additional research in this field.