A new analytical method development based on solid phase extraction (SPE) combined with high performance liquid chromatography (HPLC) was carried out. The optimum working conditions were obtained based on selection of 250 mL sample loading, 0.25 µL methanol as reconstitution solvent, 100% methanol as mobile phase and 270 nm as the optimum wavelength. Good linearity was obtained in the range of 0.015 -400 mg/L and the regression coefficient, R 2 , was 0.995. Limit of detection and quantification were calculated at LOD = 0.06 µg/L and LOQ = 0.2 µg/L respectively. Repeatability and robustness has showed good performance with low relative standard deviation less than 3.29% and 3.50% respectively. Time-of-flight mass spectrometry (TOF/MS) instrument was used to confirm that caffeine is definitely present in surface water with level of concentration ranged from 31.7 to 50.1 µg/L. All results were analyzed statistically using one-way ANOVA, Tukey with interval confidence 95% and P-value 0.05.Keywords: caffeine, stimulant, emerging pollutant, water quality, time of flight/mass spectrometry Abstrak Pembangunan kaedah analisis baru berasaskan pengekstrakan fasa pepejal bersama kromatografi cecair prestasi tinggi (KPCT) telah dijalankan. Kaedah optimum diperolehi berdasarkan tetapan iaitu 250 mL muatan sampel, 0.25 µL metanol sebagai pelarut, 100% methanol sebagai fasa bergerak dan 270 nm panjang gelombang yang optimum. Nilai kelinearan baik diperolehi pada julat kepekatan 0.015 -400 mg/L dan nilai pekali regresi, R 2 ialah 0.995. Had pengesanan dan kuantifikasi dihitung masing -masing pada LOD = 0.06 µg/L and LOQ = 0.2 µg/L. Kebolehulangan dan keteguhan kaedah menunjukkan prestasi baik dengan nilai sisihan piawai relatif yang rendah iaitu masing -masing kurang daripada 3.29% dan 3.50%. Spektrometri jisim masa penerbangan (TOF/MS) digunakan untuk mengesahkan kehadiran kafein di permukaan air dengan aras kepekatan antara julat 31.7 hingga 50.1 µg/L. Keputusan dianalisa mengunakan pendekatan statistik seperti ANOVA satu hala, Tukey dengan aras keyakinan 95% and nilai p 0.05.Kata kunci: kafein, perangsang, pencemar baru, kualiti air, spektrometri jisim/masa penerbangan