Understanding light transportation in skin tissues can help improve clinical efficacy in the laser treatment of dermatosis, such as port-wine stains (PWS). Patient-specific cross-bridge PWS vessels are structurally complicated and considerably influence laser energy deposition due to shading effects. The shading effect of PWS vessels is investigated using a tetrahedron-based Monte Carlo (MC) method with extended boundary condition (TMCE). In TMCE, body-fitted tetrahedra are generated in different tissues, and the precision of photon–surface interaction can be considerably improved via mesh refinement. Such improvement is difficult to achieve with the widely used voxel-based MC method. To fit the real physical boundary, the extended boundary condition is adapted by extending photon propagation to the semi-infinite tissue layers while restricting the statistics of photon propagation in the computational domain. Results indicate that the shading parameters, such as the cross angle, vessel distance, and geometric shadow (GS), of cross-bridge blood vessel pairs determine the peak characteristics of photon deposition in deep vessels by affecting the relative deposition of collimated and diffused light. Collimated light is shaded, attenuated, and partially transformed into diffused light due to the increase in vessel distance and GS of vessel pairs, resulting in difficulty in treating deep and shallow vessels with one laser pulse. The TMCE method can be used for the individualized and precise forecasting of laser energy deposition based on the morphology and embedding characteristics of vascular lesions.