Studying nanomaterial piezoelectricity and triboelectricity is attractive for energy and sensing applications. However, quantitative characterisation of electromechanical effects in nanomaterials is challenging due to practical limitations and possible combination of effects, resulting in contradicting reports at times. When it comes to piezoelectricity at the nanoscale, piezoresponse force microscopy (PFM) is the default characterisation tool. In PFM the converse piezoelectric effect is measured - the conversion from electrical signal to mechanical response. However, there is an underlying desire to measure the direct piezoelectric effect - conversion of mechanical deformation to an electrical signal. This corresponds to energy harvesting and sensing. Here we present time-resolved open-circuit conductive atomic force microscopy (cAFM) as a new methodology to carry out direct electromechanical characterisation. We show, both theoretically and experimentally, that the standard short-circuit cAFM mode is inadequate for piezoelectric characterisation, and that resulting measurements are governed by competing mechanisms. We apply the new methodology to nanowires of GaAs, an important semiconductor, with relatively low piezoelectric coefficients. The results suggest that time-resolved operation distinguishes between triboelectric and piezoelectric signals, and that by measuring the open-circuit voltage rather than short-circuit current, the new methodology allows quantitative characterisation of the vertical piezoelectric coefficient. The result for GaAs nanowires, ∼ 1-3 pm V-1, is in good agreement with existing knowledge and theory. This method represents a significant advance in understanding the coexistence of different electromechanical effects, and in quantitative piezoelectric nanoscale characterisation. The easy implementation will enable better understanding of electromechanics at the nanoscale.