Electrochemical decarboxylation of secondary, let alone primary carboxylic acids, is considered extremely challenging even in these state-of-the-art protocols. The recently developed rapid alternating polarity (rAP) variant of the Kolbe reaction is a notable exception as it enables decarboxylation of primary carboxylic acids with high chemoselectivity; however, this reaction favors carbon radical formation over the carbocation. To the best of our knowledge, a general electrochemical decarboxylative olefination has yet to be described. In this communication, we disclose a modification of the rAP-Kolbe conditions, now allowing facile decarboxylation of unactivated primary, secondary, and tertiary carboxylic acids without the need for preactivation (e. g., redox-active ester formation), enabling access to olefins via carbocations. Our preliminary studies started from slightly modified electrochemical decarboxylations for etherification and flurionation 15 (Table ). In an attempt to favor olefination, the alcohol nucleophile was excluded from the etherification conditions (entry 1). However, oxidation of the model secondary acid was sluggish, and no olefin product was observed. Fluorination conditions led to trace conversion to olefin 1, in good agreement with the original report that this method is not applicable to secondary carboxylic acids (entry 2). rAP Kolbe conditions gave much better conversion when compared to the previous methods, resulting in moderate yield of 1 (entry 3). To further improve the reaction, graphite electrodes were evaluated based on their well-established ability to access carbocations over carbon radicals. However, switching to graphite electrodes resulted in low conversion with 50 ms rAP (entry 4). This large drop in conversion could be explained by the order of magnitude higher electrode capacitance of graphite over reticulated vitreous carbon (RVC) (i.e., electricity was largely consumed by charge-discharge cycles of the electrical double layer). To account for such a large electrode capacitance, a much longer pulse was applied (5 s instead of 50 ms), resulting in a significant improvement in conversion and 67% yield of the desired olefin (entry 5). These conditions outperform state-of-the-art photochemical methods (entry 6), and as illustrated below, this functional electrochemical protocol enables unprecedented scalability (up to 1 kg) in the context of decarboxylative olefination of unactivated carboxylic acids. Remarkably, these optimized conditions did not work (on preparative scale) if direct current (DC) electrolysis was applied instead of alternating polarity. In fact, no conversion was observed under DC conditions (entry 7, mechanistic studies vide infra). A catalytic amount of base is necessary to ensure conversion of carboxylic acid 2 (entry 8). Use of tetramethylammonium salts can be circumvented by replacement with KOH (entry 9). Furthermore, the addition of pivalic acid is necessary to avoid partial oxidative degradation of the olefin product (entry 10). 2-Methyl-2-butene can also be used in place of pivalic acid (entry 11), further confirming the role of PivOH as a sacrificial additive rather than a pH buffering agent due to its acidic nature. With optimized conditions in hand, the scope of this electrochemical decarboxylative olefination was explored. In general, this practical method is applicable to a variety of unactivated secondary, tertiary, and even primary carboxylic acids as illustrated in Table . Compatible functional groups include: esters (3, 10, 11, 20), ketals (4), sulfones (5), carbamates (6, 7), amides (10), epoxides (11), arenes (12, 16), alcohols (14), alkenes (14, 19) and ketones (15). As demonstrated in 3-7, this method offers rapid access to unsaturated six-membered rings with a variety of functional groups.