Porous LiMn2O4 thick-film cathodes for Li-ion microbatteries are realized by laser-printing. The porous structure of the printed composite cathode consisting of active powder, binder, carbon black and graphite enables ionic and electronic transport through 50–60 μm thick electrodes due to its high intrinsic active surface area. In order to further improve the cycle stability and capacity retention of the laser-printed thick-film cathodes for discharging rates up to 1 C, laser-printed thick films are first calendered in a press and then structured using ultrafast femtosecond-laser radiation in order to form three-dimensional (3D) cathode architectures. It is shown that calendered/laser structured cathodes in the form of rectangular 3D grids exhibit discharge capacity retention of 68% at a 1 C rate, while calendered but unstructured cathodes retain only about 45% of their initial capacity at the same discharge rate. Overall, the improved discharge capacity retention and reduced degradation during later cycles can be attributed to the combination of increased electrical contact with shortened Li-ion pathways.