Multifunctional three-dimensional heterostructures for flexible electronics have gained significant attention due to their distinctive structural formability and superior electronic and optoelectronic properties. Nevertheless, conventional fabrication techniques have yet to be optimized for flexible substrates. In this study, a straightforward fiber laser direct writing (FLDW) process is demonstrated for the simultaneous fabrication of diodes (PN junctions) and bipolar junction transistors (BJTs) on flexible polyimide substrates, which is realized through the deposition of multifunctional p- or n-type copper oxide films (CuOx) and p- or n-type porous laser-reduced graphene oxide films (LrGO) using fiber laser ablation and deposition. The presence of both p- and n-type semiconductor films is confirmed through material characterization. The fabricated PN junctions exhibit reasonable diode rectification ratios, ranging from 20 to 220, and perform reliably under numerous operating conditions such as light-dark illumination and elevated temperatures. Furthermore, I-V curve analysis indicates that the current gain and electrical performance of printed negative-positive-negative (NPN) (or positive-negative-positive, PNP) BJTs can be tailored by adjusting the laser energy density of the FLDW process and the base gap width of the BJTs. As a proof of concept, the FLDW process is successfully employed to deposit both NPN (or PNP) BJTs composed of LrGO/CuOx heterostructures with controlled current gains. Its ease of operation, versatility, and cost-effectiveness make FLDW promising for large-scale flexible electronics fabrication.