Laser assisted electrochemical machining with tube electrode (LAECM-TE) is a hybrid small hole machining method which combines the advantages of electrochemical machining (ECM) and laser beam machining (LBM). It has great advantages in improving the aspect ratio and reducing the taper of small-holes. However, the hybrid tool electrode currently used by LAECM-TE is a two-thick-layer tube an outer conductive metal layer as the ECM cathode and an inner nonconductive layer for laser guiding. This makes it difficult to machine micro-holes and affects the effect of electrolyte flushing. If the metal tube is directly used to transmit laser, the inner wall is not as smooth as quartz glass tube, which will produce large transmission loss. In this study, a chemical polishing method of metal capillary inner wall for LAECM-TE is proposed, which does not need a sleeve, so the electrode size can be further reduced. The processing performance of inner wall polished capillary is preliminarily verified by experiments, which can give play to the beneficial effect of laser and expand the boundary of LAECM-TE.