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Lipoprotein(a) [Lp(a)] is a useful marker for cardiovascular risk stratification. Previous studies have shown higher Lp(a) levels in women than in men and sex differences in its association with atherosclerosis. The aim of this study was to assess associations between Lp(a) levels and cardiovascular disease (CVD) in men and women with suspected familial hypercholesterolemia (FH). The study included 220 hypercholesterolemic patients (110 men) treated at an outpatient lipid clinic. Clinical data, anthropometric measurements, and laboratory tests were collected. Lipid concentrations were measured enzymatically and Lp(a) by latex-enhanced immunonephelometry. Coronary artery disease (CAD) was present in 27.3% of men and 14.5% of women; 30.9% were current smokers and 84.5% received statin therapy. Median Lp(a) levels were significantly higher in women with CAD than without CAD, whereas no significant difference was observed in men. After age standardization, mean Lp(a) levels did not differ by CAD status in either sex. In age-adjusted logistic regression, CAD in men was associated with smoking and hypertension, while in women it was associated with LDL-C, Lp(a), and smoking. These findings support sex-specific differences in the role of Lp(a) in CAD development and identify Lp(a) as a CVD risk factor in hypercholesterolemic women.