In this work, the electrochemical response of different morphologies (shapes) and dimensions of additively manufactured (3D-printing) carbon black (CB)/poly-lactic acid (PLA) electrodes are reported. The working electrodes (WE) are printed using standard non-conductive PLA based filament for the housing and commercial Protopasta (carbon black/PLA) filament for the electrode and connection parts. Discs, squares, equilateral triangles and six-point stars with varying working electrode (WE) widths from 2 to 10 mm are evaluated herein towards the well-known near-ideal outer sphere redox probe hexaamineruthenium(III) chloride (RuHex). The results obtained show that triangular and squared electrodes exhibit a faster heterogeneous electron transfer (HET) rate constant (k°) than those of discs and stars, the latter being the slowest one. The results reported here also show a trend between the WE dimension and the reversibility of the electrochemical reaction, which decreases as the WE size increases. It is also observed that the ratio of the geometrical and electroactive area (%realarea) decreases as the overall WE size increases. On the other hand, these four WE shapes were applied toward the well-known and benchmarking detection of ascorbic acid (AA), uric acid (UA), β-nicotinamide adenine dinucleotide (NADH) and dopamine (DA). Moreover, electroanalytical detection of real acetaminophen (ACOP) samples is also showcased. The different designs for the working electrode proposed in this manuscript are easily changed to any other desired shapes thanks to the additive manufacturing methodology, these four shapes being just an example of what additive manufacturing can offer to experimentalists and to electrochemists in particular. Additive manufacturing is shown here as a versatile and rapid prototyping tool for the production of novel electrochemical sensing platforms, with scope for this work to be able to impact a wide variety of electroanalytical applications.