Diamond coatings were deposited on PCB (printed circuit board) carbide milling tool substrates under various schemes of acid and alkali pretreatment by hot filament chemical vapor deposition (HFCVD). Scanning electron microscopy and X-ray coating analysis were used to examine the surface morphology of the milling tools and the impact of de-cobalt from the substrate surface after pretreatment. Milling experiments were carried out to study the cutting performance of diamond-coated PCB micro-milling tools under various pretreatment processes. The results show that abrasive wear, coating flaking, and cutting-edge chipping are the main failure forms of coated PCB milling tools. The substrate pretreatment process with 20 min of alkali etching followed by 20 s of acid etching allows the diamond-coated micro-milling tools to produce the best film–substrate adhesion and substrate strength. These milling tools also have the longest service lives and are suitable for the high-speed cutting processing of PCB.