How to join on multiple columns in Pyspark?

You should use & / | operators and be careful about operator precedence (== has lower precedence than bitwise AND and OR):

df1 = sqlContext.createDataFrame(
    [(1, "a", 2.0), (2, "b", 3.0), (3, "c", 3.0)],
    ("x1", "x2", "x3"))

df2 = sqlContext.createDataFrame(
    [(1, "f", -1.0), (2, "b", 0.0)], ("x1", "x2", "x3"))

df = df1.join(df2, (df1.x1 == df2.x1) & (df1.x2 == df2.x2))
df.show()

## +---+---+---+---+---+---+
## | x1| x2| x3| x1| x2| x3|
## +---+---+---+---+---+---+
## |  2|  b|3.0|  2|  b|0.0|
## +---+---+---+---+---+---+