The thermal conductivity of organic superconductor κ-(BEDT-TTF)2Cu(NCS)2 (Tc=10.4 K) has been studied in a magnetic field rotating within the 2D superconducting planes with high alignment precision. At low temperatures (T < ∼ 0.5 K), a clear fourfold symmetry in the angular variation, which is characteristic of a d-wave superconducting gap with nodes along the directions rotated 45 • relative to the b and c axes of the crystal, was resolved. The determined nodal structure is inconsistent with recent theoretical predictions of superconductivity induced by the antiferromagnetic spin fluctuation. 74.20.Rp, 74.25.Fy, 74.25.Jb, 74.70.Kn Since the discovery of superconductivity in organic materials about 2 decades ago, the question of the pairing symmetry among this class of materials is one of the most intriguing problems. In particular, the nature of the superconductivity in quasi-2D κ-(BEDT-TTF) 2 X salts (κ-(ET) 2 X), where the ion X can, for example, be Cu(SCN) 2 , Cu[N(CN) 2 ]Br or I 3 , has attracted considerable attention. In these layered organics, Shubnikov-de Haas oscillation experiments have established the existence of a well-defined Fermi surface (FS), demonstrating the Fermi liquid character of the low energy excitation. The large enhancement of the effective mass revealed by the specific heat as well as magnetic susceptibility measurements suggests the strong electron correlation effect in the normal state. Moreover, it was suggested that superconductivity occurs in proximity to the antiferromagnetic (AF) ordered state in the phase diagram [1]. Since some of these unusual properties suggest analogies with high-T c cuprates [2], it was pointed out by many authors that the AF spin-fluctuation should play an important role for the occurrence of superconductivity [3,4].Unconventional superconductivity is characterized by a superconducting gap with nodes along certain crystal directions. Since the superconducting gap structure is intimately related to the pairing interaction, its identification is crucial for understanding the pairing mechanism. Although the structure of the superconducting order parameter of κ-(ET) 2 X salts has been examined by several techniques, it is still controversial as we now summarize [1]. Results strongly in favor of unconventional pairing symmetry came from NMR experiments of κ-(ET) 2 Cu[N(CN) 2 ]Br, in which the absence of the Hebel-Slichter peak and cubic T -dependence of the spin lattice relaxation rate 1/T 1 were interpreted as an indication of d-wave pairing with line nodes [1,5]. The existence of the T -linear term in the thermal conductivity at low temperatures of κ-(ET) 2 Cu(NCS) 2 also supported the presence of line nodes [6]. However, some of the specific heat and penetration depth studies on these materials led to conflicting results. For example, recent specific heat measurements reported a fully gapped superconductivity [7]. Since these measurements rely on the T -dependence of the physical quantities, it is more desirable to measure the in-plane anisotropy of th...