materials, piezoelectric materials, which can convert mechanical shape changes into electric outputs, are particularly favorable to fabricate wearable devices for mechanicalrelated sensing and power generation. [15][16][17] According to material molecular compositions, piezoelectric materials are generally divided into ceramics and polymers. Indeed, even though inorganic piezoelectric materials offer high piezoelectric property, they are mechanically hard and brittle, which have difficulties to be directly applied to wearable devices. Besides, many piezoelectric ceramics contain heavy metal elements such as lead, that are harmful to human and environment. [18][19][20] On the other hand, piezoelectric polymers, represented by polyvinylidene fluoride (PVDF) and its copolymer poly[(vinylidenefluoride-cotrifluoroethylene] (P(VDF-TrFE)), are more preferable for wearable devices as they are lightweight, stretchable, environmentfriendly and chemically stable. [21,22] To construct piezoelectric polymer fibers, electrospinning, as a representative template-free method, [23,24] is a versatile technique to produce extended length of fiber-shaped structures with a number of advantages such as large surface area, tunable surface morphologies, and enhanced mechanical performance. [25][26][27][28] With electrospinning, when the droplet of polymer solution is charged by high applied voltage, the liquid droplet is pulled into a thin fiber and then collected by the grounded electrode. However, this liquid-to-solid transferring process normally results in randomly distributed fibers with poor electrical properties and limited response to mechanical stimuli. Therefore, to improve the performance of electrospun fibers, several methods have been demonstrated to obtain aligned electrospun fibers. [29][30][31][32][33] Two most frequently adopted methods are: 1) using a high-speed rotating collector with a very sharp edge, [34][35][36] and 2) using two separated parallel electrodes. [37,38] A very high rotating speed (>3000 rpm) is necessary for the rotating collector method, which brings high requirements to the fabrication facilities and increases electricity consumption. Also, the necessary role of sharp edge further restricts the amount of highly aligned electrospun fibers that can be collected. The parallel electrode method, on the other hand, can only fabricate aligned electrospun fibers in a very limited length, typically on millimeter scale.Advances in functional fabrics enable the realization of wearable devices in the form factor of fibers that can be seamlessly adapted in our daily lives. For mechanical-related sensing and power generation, piezoelectric materials are particularly favorable because they can convert mechanical shape changes into electric outputs. Electrospinning is a widely applied technique to produce extended length of fiber-shaped piezoelectric devices. However, this versatile process normally results in randomly distributed fibers with poor electrical properties and limited response to mechanical stimuli. H...